Sample records for noble gas monitoring

The discovery in Iraq after the Gulf War of the existence of a large clandestine nuclear-weapon program has led to an across-the-board international effort, dubbed Programme 93+2, to improve the effectiveness and efficiency of International Atomic Energy Agency (IAEA) safeguards. One particularly significant potential change is the introduction of environmental monitoring (EM) techniques as an adjunct to traditional safeguards methods. Monitoring of stable noblegas (Kr, Xe) isotopic abundances at reprocessing plant stacks appears to be able to yield information on the burnup and type of the fuel being processed. To estimate the size of these signals, model calculations of the production of stable Kr, Xe nuclides in reactor fuel and the subsequent dilution of these nuclides in the plant stack are carried out for two case studies: reprocessing of PWR fuel with a burnup of 35 GWd/tU, and reprocessing of CAND fuel with a burnup of 1 GWd/tU. For each case, a maximum-likelihood analysis is used to determine the fuel burnup and type from the isotopic data.

This is the final report of a two-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The perceived importance of measuring the xenon and krypton isotopics of nuclear activities has increased substantially in recent years. We have performed a systems analysis and theoretical simulation of the production, atmospheric dispersion, and isotopic abundances of noble-gas fission products, addressing several questions of interest, including: the relative isotopic variation as a function of nuclear fuel composition, reactor operational history, reactor type, distance from stack, and ambient meteorological conditions. Of particular importance in this analysis was the question of back-calculating process parameters of interest given noble-gas isotopic data. An analysis of the effect of measurement uncertainties was also performed. The results of these analyses indicate that this monitoring concept should be experimentally feasible.

An environmental monitoring technique using analysis of stable noblegas isotopic ratios on-stack at a reprocessing facility was developed. This technique integrates existing technologies to strengthen safeguards at reprocessing facilities. The isotopic ratios are measured using a mass spectrometry system and are compared to a database of calculated isotopic ratios using a Bayesian data analysis method to determine specific fuel parameters (e.g., burnup, fuel type, fuel age, etc.). These inferred parameters can be used by investigators to verify operator declarations. A user-friendly software application (named NOVA) was developed for the application of this technique. NOVA included a Visual Basic user interface coupling a Bayesian data analysis procedure to a reactor physics database (calculated using the Monteburns 3.01 code system). The integrated system (mass spectrometry, reactor modeling, and data analysis) was validated using on-stack measurements during the reprocessing of target fuel from a U.S. production reactor and gas samples from the processing of EBR-II fast breeder reactor driver fuel. These measurements led to an inferred burnup that matched the declared burnup with sufficient accuracy and consistency for most safeguards applications. The NOVA code was also tested using numerous light water reactor measurements from the literature. NOVA was capable of accurately determining spent fuel type, burnup, and fuel age for these experimental results. Work should continue to demonstrate the robustness of this system for production, power, and research reactor fuels.

A Georgia Institute of Technology/Argonne National Laboratory team will develop and demonstrate novel ultrahigh sensitivity heavy noblegas (krypton, xenon, and radon) detectors for long-term monitoring of spent fuel and TRU waste, as well as for distinguishing background radon a...

Precise measurements of a precessional rate of noblegas in a magnetic field is obtained by constraining the time averaged direction of the spins of a stimulating alkali gas to lie in a plane transverse to the magnetic field. In this way, the magnetic field of the alkali gas does not provide a net contribution to the precessional rate of the noblegas.

Environmental monitoring of shale gas production and geological carbon dioxide (CO2) storage requires identification of subsurface gas sources. Noble gases provide a powerful tool to distinguish different sources if the modifications of the gas composition during transport can be accounted for. Despite the recognition of compositional changes due to gas migration in the subsurface, the interpretation of geochemical data relies largely on zero-dimensional mixing and fractionation models. Here we present two-phase flow column experiments that demonstrate these changes. Water containing a dissolved noblegas is displaced by gas comprised of CO2 and argon. We observe a characteristic pattern of initial co-enrichment of noble gases from both phases in banks at the gas front, followed by a depletion of the dissolved noblegas. The enrichment of the co-injected noblegas is due to the dissolution of the more soluble major gas component, while the enrichment of the dissolved noblegas is due to stripping from the groundwater. These processes amount to chromatographic separations that occur during two-phase flow and can be predicted by the theory of gas injection. This theory provides a mechanistic basis for noblegas fractionation during gas migration and improves our ability to identify subsurface gas sources after post-genetic modification. Finally, we show that compositional changes due to two-phase flow can qualitatively explain the spatial compositional trends observed within the Bravo Dome natural CO2 reservoir and some regional compositional trends observed in drinking water wells overlying the Marcellus and Barnett shale regions. In both cases, only the migration of a gas with constant source composition is required, rather than multi-stage mixing and fractionation models previously proposed.

A prototype of a calibration facility for noblegasmonitoring using (41)Ar in the PTKMR-BATAN has been tested. The facility was designed in such a way that the standard source of gas can be reused. The radioactive (41)Ar source was obtained by thermal neutron reaction of (40)Ar(n, γ)(41)Ar using a thermal neutron flux of 4.8×10(13) neutrons per cm(2) per second in two minutes on the multipurpose G.A. Siwabessy Reactor (Batan, Serpong, Indonesia). Gamma spectrometry was used to measure the radioactivity and purity of (41)Ar. The spectrum of the (41)Ar observed yields an energy of 1294 keV because of the highest intensity (99.2%). The activity of (41)Ar was 2821 kBq and 4% of the expanded uncertainty. The time required for (41)Ar to reach homogeneity was 7 min, and the effectiveness of resuse was 53%. PMID:22516716

The primary objective of this research project is to develop heavy noblegas (krypton, xenon, and radon) detectors for (1) long-term monitoring of transuranic waste, spent fuel, and other uranium and thorium bearing wastes and (2) alpha particle air monitors that discriminate between radon emissions and other alpha emitters. A University of Cincinnati/Argonne National Laboratory (UC/ANL) Team was assembled to complete this detector development project. DOE needs that are addressed by this project include improved long-term monitoring capability and improved air monitoring capability during remedial activities. Successful development and implementation of the proposed detection systems could significantly improve current capabilities with relatively simple and inexpensive equipment.

A noblegasmonitoring system has been installed at Ontario Power Generation's Pickering Nuclear Generating Station (PNGS) near Toronto, Canada. This monitoring system allows a direct measure of air kerma from external radiation instead of calculating this based on plant emission data and meteorological models. This has resulted in a reduction in the reported effective dose from external radiation by a factor of at least ten. The system consists of nine self-contained units, each with a 7.6 cm x 7.6 cm (3 inch x 3 inch) NaI(TI) detector that is calibrated for air kerma. The 512-channel gamma ray spectral information is downloaded daily from each unit to a central computer where the data are stored and processed. A spectral stripping procedure is used to remove natural background variations from the spectral windows used to monitor xenon-133 (133Xe), xenon-135 (135Xe), argon-41 (41Ar), and skyshine radiation from the use of radiography sources. Typical monthly minimum detection limits in air kerma are 0.3 nGy for 133Xe, 0.7 nGy for 35Xe, 3 nGy for 41Ar and 2 nGy for skyshine radiation. Based on 9 months of continuous operation, the annualised air kerma due to 133Xe, 135Xe and 41Ar and skyshine radiation were 7 nGy, 8 nGy, 26 nGy and 107 nGy respectively. PMID:11605799

The original thrust of our Genesis funding was to extend and refine the noblegas analytical capabilities of this laboratory to improve the precision and accuracy of noblegas measurements in order to optimize the scientific return from the Genesis Mission. This process involved both instrumental improvement (supplemented by a SRLIDAP instrument grant) and refinement of technique. The Genesis landing mishap shifted our emphasis to the irregular aluminum heat shield material from the flat collector wafers. This has required redesign of our laser extraction cells to accommodate the longer focal lengths required for laser extraction from non-flat surfaces. Extraction of noble gases from solid aluminum surfaces, rather than thin coatings on transparent substrates has required refinement of controlled-depth laser ablation techniques. Both of these bring new problems, both with potentially higher blanks form larger laser cells and the larger quantities of evaporated aluminum which can coat the sapphire entrance ports. This is mainly a problem for the heavy noble gases where larger extraction areas are required, necessitating the new aluminum vapor containment techniques described below. With the Genesis Mission came three new multiple multiplier noblegas mass spectrometers to this laboratory, one built solely by us (Supergnome-M), one built in collaboration with Nu-Instruments (Noblesse), and one built in collaboration with GVI (Helix). All of these have multiple multiplier detection sections with the Nu-Instruments using a pair of electrostatic quad lenses for isotope spacing and the other two using mechanically adjustable positions for the electron multipliers. The Supergnome-M and Noblesse are installed and running. The GVI instrument was delivered a year late (in March 2005) and is yet to be installed by GVI. As with all new instruments there were some initial development issues, some of which are still outstanding. The most serious of these are performance issues

We present a theoretical basis for reconstructing paleotemperatures from the open-system behavior of cosmogenic noble gases produced in minerals at Earth's surface. Experimentally-determined diffusion kinetics predicts diffusive loss of cosmogenic 3He and 21Ne from common minerals like quartz and feldspars at ambient temperatures; incomplete retention has also been observed empirically in field studies. We show that the theory of simultaneous production and diffusion that applies to radiogenic noble gases in minerals-the basis of thermochronology-can also be applied to cosmogenic noble gases to reconstruct past surface temperatures on Earth. We use published diffusion kinetics and production rates for 3He in quartz and 21Ne in orthoclase to demonstrate the resolving power of cosmogenic noblegas paleothermometry with respect to exposure duration, temperature, and diffusion domain size. Calculations indicate that, when paired with a quantitatively retained cosmogenic nuclide such as 21Ne or 10Be, observations of cosmogenic 3He in quartz can constrain temperatures during surface exposure in polar and high altitude environments. Likewise, 21Ne retention in feldspars is sensitive to temperatures at lower latitudes and elevations, expanding the potential geographic applicability of this technique to most latitudes. As an example, we present paired measurements of 3He and 10Be in quartz from a suite of Antarctic sandstone erratics to test whether the abundances of cosmogenic 3He agree with what is predicted from first principles and laboratory-determined diffusion kinetics. We find that the amounts of cosmogenic 3He present in these samples are consistent with the known mean annual temperature (MAT) for this region of Antarctica between -25 and -30 °C. These results demonstrate the method's ability to record paleotemperatures through geologic time.

Noblegas NMR detected by alkali co-magnetometers has the potential for measurement of precession frequencies at the pHz level. This is done by eliminating the dominant known sources of systematic errors: alkali frequency shifts and quadrupole shifts. We present results of successful synchronous pumping of noblegas nuclei and measurements of alkali co-magnetometer sensitivity levels that project a 131-Xe noise level of 100 nHz /√{ Hz} . Future dual noble-gas co-magnetometry promises to improve the noise level by a factor of 10 or more. This research is supported by the NSF and Northrop-Grumman Corp.

Trapping of noble gases by carbon-rich matter was investigated by synthesizing carbon condensates in a noblegas atmosphere. Laser evaporation of a solid carbon target yielded submicron grains which proved to be efficient noblegas trappers (Xe distribution coefficients up to 13 cu cm STP/g-atm). The carbon condensates are better noblegas trappers than previously reported synthetic samples, except one, but coefficients inferred for meteoritic acid-residues are still orders of magnitude higher. The trapped noble gases are loosely bound and elementally strongly fractionated, but isotopic fractionations were not detected. Although this experiment does not simulate nebular conditions, the results support the evidence that carbon-rich phases in meteorites may be carriers of noble gases from early solar system reservoirs. The trapped elemental noblegas fractionations are remarkably similar to both those inferred for meteorites and those of planetary atmospheres for earth, Mars and Venus.

Noble gases in groundwater appear to offer a practical approach for quantitatively determining past surface air temperatures over recharge areas for any watershed. The noblegas temperature (NGT) proxy should then permit a paleothermometry of a region over time. This terrestria...

Fractionated noblegas relative abundances (Ne/Ar, Kr/Ar and Xe/Ar) and isotopic compositions (40Ar/36Ar, 38Ar/36Ar, 20Ne/22Ne, 21Ne/22Ne) are found in volcanic materials, notably in pumices (1-3). This has generally been interpreted as fractionation resulting from diffusion. However, there is some disagreement as to whether this fractionation occurs during high temperature magmatic processes (3) or due to diffusion of air into solidified pyroclastic deposits (2). We show that differences in relative noblegas diffusivities (e.g. D4He vs D40Ar, where D is the diffusivity) and isotopic diffusivities (e.g. D40Ar vs D36Ar) reduce at high temperatures (Fig). These results predict minimal fractionation of noble gases during magmatic processes. However, it is important to note that these diffusivities were measured in silicate glasses; the relative noble diffusivities in silicate liquids are poorly known. We have developed a new experimental protocol which will to determine the diffusivities of the noble gases and their isotopes in the liquid state. A graphite crucible c. 0.3 mm diameter and c. 20mm deep is filled with powdered glass of the desired composition, heated to 1773 K for 15 minutes and quenched to form a glass cylinder within the crucible. The crucible is then placed in a low pressure (1 bar) controlled atmosphere vertical furnace and heated at high temperatures (1673-1773K) for 2 hours in a pure N2 atmosphere. At this point noble gases (He and Ar) are introduced into the furnace and allowed to diffuse into the cylinder of liquid for durations of between 30 and 90. After quenching, the glass cylinder, preserving its' diffusion profile, is sawed into c. 1mm thick discs which are measured by conventional noblegas mass spectrometry for noblegas abundances (He, Ar) and isotopes (40,38,36Ar). The results will be presented at the conference. References 1 Kaneoka, I. Earth Planet Sci Letts 48, 284-292 (1980). 2 Pinti, D. L., Wada, N. & Matsuda, J. J. Volcan

Modern physics usually pictures the nuclear structure as about sphere and treats various detailed situation as perturbative, which may be obscured. In addition, the explanation why 235U undergoes nuclear fission and 238U does not is too difficult and unclear for the people to understand. However, in this paper, we introduce a new approach on the nuclear structure of the noblegas, which simultaneously can explain several phenomena that is obscurely elucidated by modern physics. We consider a 1:1 ratio between protons and neutrons and need the concept of the symmetry of the nuclear structure, because the electron's shell of the noblegas is fully occupied. From these, we can predict the number of neutrons of each noblegas exactly

The composition of noble gases in both gas and water samples collected from Horseshoe Spring, Yellowstone National Park, was found to be depth dependent. The deeper the sample collection within the spring, the greater the enrichment in Kr, Xe, radiogenic {sup 4}He, and {sup 40}Ar and the greater the depletion in Ne relative to {sup 36}Ar. The compositional variations are consistent with multi-component mixing. The dominant component consists of dissolved atmospheric gases acquired by the pool at the surface in contact with air. This component is mixed in varying degree with two other components, one each for gas and water entering the bottom of the pool. The two bottom components are not in equilibrium. In Horseshoe Spring, the bubbles entering at the bottom strip the atmospheric-derived pool gases from the surrounding water while en route to the surface. If the original bottom bubbles are noblegas, as in the case of Horseshoe, the acquired pool gases can then quickly obliterate the original bubble composition. These results are used to demonstrate that Yellowstone spring surface gas samples, and perhaps similarity sampled thermal springs from other hydrothermal systems, have gas abundances that depend more on spring morphology than processes occurring deeper in the hydrothermal system.

An investigation of the solubilities of the noble gases from synthesis and solubility studies of the sheet silicate mineral serpentine in carbonaceous chondrites is presented. Hydrothermal synthesis and exchange experiments were made at 340C and 1 kbar with noblegas partial pressures from 2 times 10 to the -8th power to 0.1 atm. The measured distribution coefficients for noble gases are not sufficiently high to account for the trapped noble gases in carbonaceous chondrites by exchange in solar nebula if meteoritic minerals have comparable distribution coefficients. Also, serpentine gains and loses noble gases to approach equilibrium values with the terrestrial atmosphere, indicating that this exposure may have influenced the noblegas abundances in phyllosilicate minerals of these chondrites. The dispersion of K-Ar ages of carbonaceous chondrites could be the result of phyllosilicates approaching equilibrium solubility of atmospheric Ar-40.

A method and system for storing and delivering a noblegas for an ion propulsion system where an adsorbent bearing a noblegas is heated within a storage vessel to desorb the noblegas which is then flowed through a pressure reduction device to a thruster assembly. The pressure and flow is controlled using a flow restrictor and low wattage heater which heats an adsorbent bed containing the noblegas propellant at low pressures. Flow rates of 5-60 sccm can be controlled to within about 0.5% or less and the required input power is generally less than 50 W. This noblegas storage and delivery system and method can be used for earth orbit satellites, and lunar or planetary space missions.

The mechanisms responsible for noblegas concentrations, abundance patterns, and strong retentivity in sedimentary lithologies remain poorly explained. Diffusion-controlled fractionation of noble gases is modeled and examined as an explanation for the absolute and relative abundances of noble gases observed in sediments. Since the physical properties of the noble gases are strong functions of atomic mass, the individual diffusion coefficients, adsorption coefficients and atomic radii combine to impede heavy noblegas (Xe) diffusion relative to light noblegas (Ne) diffusion. Filling of lithic grains/half-spaces by diffusive processes thus produces Ne enrichments in the early and middle stages of the filling process with F(Ne) values similar to that observed in volcanic glasses. Emptying lithic grains/half-spaces produces a Xe-enriched residual in the late (but not final) stages of the process producing F(Xe) values similar to that observed in shales. 'Exotic but unexceptional' shales that exhibit both F(Ne) and F(Xe) enrichments can be produced by incomplete emptying followed by incomplete filling. This mechanism is consistent with literature reported noblegas abundance patterns but may still require a separate mechanism for strong retention. A system of labyrinths-with-constrictions and/or C-, Si-nanotubes when combined with simple adsorption can result in stronger diffusive separation and non-steady-state enrichments that persist for longer times. Enhanced adsorption to multiple C atoms inside C-nanotubes as well as dangling functional groups closing the ends of nanotubes can provide potential mechanisms for 'strong retention'. We need new methods of examining noble gases in rocks to determine the role and function of angstrom-scale structures in both the diffusive enrichment process and the 'strong retention' process for noblegas abundances in terrestrial rocks.

The recent experiment and theoretical results obtained for noblegas nuclear laser systems are presented. It is shown that the noblegas lasers are among the easiest systems to pump by nuclear excitation and as a result, all of the noble gases except He have lased under nuclear excitation. The noblegas systems are not ideal for high-power applications but they do give valuable insight into the operation and pumping mechanisms associated with nuclear lasers. At present, the Ar-Xe system is the best noblegas candidate for (U-235)F6 pumping. It appears that the quenching of Ar-Xe lasing is a result of the fluorine and not the uranium or fission fragments themselves. Thus, to achieve lasing with UF6, a fluorine compatible system must be found.

Thermal neutron detection is of vital importance to many disciplines, including neutron scattering, workplace monitoring, and homeland protection. We survey recent results from our collaboration which couple low-pressure noblegas scintillation with novel approaches to neutron absorbing materials and geometries to achieve potentially advantageous detector concepts. Noblegas scintillators were used for neutron detection as early as the late 1950's. Modern use of noblegas scintillation includes liquid and solid forms of argon and xenon in the dark matter and neutron physics experiments and commercially available high pressure applications have achieved high resolution gamma ray spectroscopy. Little attention has been paid to the overlap between low pressure noblegas scintillation and thermal neutron detection, for which there are many potential benefits.

Theoretical calculations have been performed to determine the spectroscopic constant for the ground and selected low-lying electronic states of the transition-metal noble-gas ions Var(+), FeAr(+), CoAr(+), CuHe(+), CuAr(+), and CuKr(+). Analogous calculations have been performed for the ground states of the alkali noble-gas ions LiAr(+), LiKr(+), NaAr(+), and KAr(+) and the alkaline-earth noble-gas ion MgAr(+) to contrast the difference in binding energies between the simple and transition-metal noble-gas ions. The binding energies increase with increasing polarizability of the noble-gas ions, as expected for a charge-induced dipole bonding mechanism. It is found that the spectroscopic constants of the X 1Sigma(+) states of the alkali noble-gas ions are well described at the self-consistent field level. In contrast, the binding energies of the transition-metal noble-gas ions are substantially increased by electron correlation.

Magnetic resonance imaging using the MR signal from hyperpolarized noble gases 129Xe and 3He may become an important new diagnostic technique. Alex Pines (adapting the hyperpolarization technique pioneered by William Happer) presented MR spectroscopy studies using hyperpolarized 129Xe. The current authors recognized that the enormous enhancement in the detectability of 129Xe, promised by hyperpolarization, would solve the daunting SNR problems impeding their attempts to use 129Xe as an in vivo MR probe, especially in order to study the action of general anesthetics. It was hoped that hyperpolarized 129Xe MRI would yield resolutions equivalent to that achievable with conventional 1H 2O MRI, and that xenon's solubility in lipids would facilitate investigations of lipid-rich tissues that had as yet been hard to image. The publication of hyperpolarized 129Xe images of excised mouse lungs heralded the emergence of hyperpolarized noble-gas MRI. Using hyperpolarized 3He, researchers have obtained images of the lung gas space of guinea pigs and of humans. Lung gas images from patients with pulmonary disease have recently been reported. 3He is easier to hyperpolarize than 129Xe, and it yields a stronger MR signal, but its extremely low solubility in blood precludes its use for the imaging of tissue. Xenon, however, readily dissolves in blood, and the T1 of dissolved 129Xe is long enough for sufficient polarization to be carried by the circulation to distal tissues. Hyperpolarized 129Xe dissolved-phase tissue spectra from the thorax and head of rodents and humans have been obtained, as have chemical shift 129Xe images from the head of rats. Lung gas 129Xe images of rodents, and more recently of humans, have been reported. Hyperpolarized 129Xe MRI (HypX-MRI) may elucidate the link between the structure of the lung and its function. The technique may also be useful in identifying ventilation-perfusion mismatch in patients with pulmonary embolism, in staging and tracking the

Presents calculations that suggest stoichiometric, ionic, and noblegas-metal compounds may be stable. Bases calculations on estimated values of electron affinity, anionic radius for the noble gases and for the Born exponents of resulting crystals. Suggests the desirability of experiments designed to prepare compounds containing anionic,…

Our recent work on He, Ne, and Ar in Alpine gold samples has demonstrated that gold is extremely retentive for He and could thus, in principle, be used for U/Th-He-4 dating. For vein-type gold from Brusson, Northern Italy, we derived a U/Th-He-4 age of 36 Ma, in agreement with the K-Ar formation age of associated muscovites and biotites. However, in placer gold from the Napf area, Central Switzerland, we observed large excesses of both He-4 and radiogenic Ar-40 (Ar-40 sub rad, defined as Ar-40-295.5-Ar-.36). The gas release systematics indicate two distinct noblegas components, one of which is released below about 800 C and the other one at the melting point of gold (1064 C). We now present results of He and Xe measurements in a 1 g placer gold sample from the river Kruempelgraben, as well as He and Ar data for Brusson vein-type gold and for gold from the Lily Gold Mine, South Africa. We calculate reasonable U/Th-He-4 as well as U-Xe ages based on those gases which are released at approximately 800 C. Probably the low-temperature components represent in-situ-produced radiogenic He and fission Xe, whereas the gases evolving when gold melts have been trapped during gold formation. Therefore, only the low-temperature components are relevant for dating purposes.

We pursued advanced technology development of laser-polarized noblegas nuclear magnetic resonance (NMR) as a novel biomedical imaging tool for ground-based and eventually space-based application. This new multidisciplinary technology enables high-resolution gas-space magnetic resonance imaging (MRI)-e.g., of lung ventilation-as well as studies of tissue perfusion. In addition, laser-polarized noble gases (3He and 129Xe) do not require a large magnetic field for sensitive detection, opening the door to practical MRI at very low magnetic fields with an open, lightweight, and low-power device. We pursued two technology development specific aims: (1) development of low-field (less than 0.01 T) noblegas MRI of humans; and (2) development of functional MRI of the lung using laser-polarized noblegas and related techniques.

In the last decade, there has been an unprecedented expansion in the development of unconventional hydrocarbon resources. Concerns have arisen about the effect of this new industry on groundwater quality, particularly focussing on hydraulic fracturing, the technique used to increase the permeability of the targeted tight shale formations. Methane contamination of groundwater has been documented in areas of gas production1 but conclusively linking this to fugitive emissions from unconventional hydrocarbon production has been controversial2. A lack of baseline measurements taken before drilling, and the equivocal interpretation of geochemical data hamper the determination of possible contamination. Common techniques for "fingerprinting" gas from discrete sources rely on gas composition and isotopic ratios of elements within hydrocarbons (e.g. δ13CCH4), but the original signatures can be masked by biological and gas transport processes. The noble gases (He, Ne, Ar, Kr, Xe) are inert and controlled only by their physical properties. They exist in trace quantities in natural gases and are sourced from 3 isotopically distinct environments (atmosphere, crust and mantle)3. They are decoupled from the biosphere, and provide a separate toolbox to investigate the numerous sources and migration pathways of natural gases, and have found recent utility in the CCS4 and unconventional gas5 industries. Here we present a brief overview of noblegas data obtained from a new coal bed methane (CBM) field, Central Scotland. We show that the high concentration of helium is an ideal fingerprint for tracing fugitive gas migration to a shallow groundwater. The wells show variation in the noblegas signatures that can be attributed to differences in formation water pumping from the coal seams as the field has been explored for future commercial development. Dewatering the seams alters the gas/water ratio and the degree to which noble gases degas from the formation water. Additionally the

Here we examine the role of slab dehydration in determining the elemental pattern of recycled noble gases. As a first step, we apply newly reported measurements of He-Ne-Ar (light noble gases) solubility and diffusivity in amphibole to parameterize a 1D diffusive-reaction transport model that simulates noblegas behavior during fluid loss from down-going oceanic crust. Recent experiments demonstrate that noble gases are highly soluble in ring-structured minerals, such as amphibole and other common hydrothermal products in slabs [1]. These results suggest that ring-structured minerals have the potential to strongly influence the budget of noble gases input into subduction zones and the elemental fractionations associated with volatile loss from slabs New measurements of He-Ne-Ar solubility in a suite of amphiboles have been completed utilizing the methodology described in [1]. These new measurements confirm that all light noble gases are highly soluble in amphibole, and that noblegas solubility correlates with the availability of unoccupied ring sites. New experimental measurements of He and Ne diffusivity have also been completed using a step-degassing approach at the Berkeley Geochronology Center. These measurements suggest that vacant ring sites in amphibole act to slow noblegas diffusion. We combine the newly acquired He and Ne diffusivity measurements with literature values for Ar diffusivity [2] to parameterize the diffusive-reaction transport model. Application of these data to the diffusive-reaction transport model yields several new insights. The relative mobility of Ne compared to Ar allows for efficient extraction of Ne from "hot" slabs by shallow depths (<50 km), while Ar is effectively retained to deeper depths, potentially past sub-arc conditions. Noblegas partition coefficients sharply increase with depth, following their increasing non-ideality in supercritical fluids, causing noble gases to partition back into minerals from any fluids retained in

D. HAMILTON*, J.B. SCHWIETERS, D. TUTTAS, M. KRUMMEN, M. DEERBERG, N.S. LLOYD1 1Thermo Fisher Scientific, Hanna-Kunath-Str. 11, 28199 Bremen, Germany (*correspondence: Doug.Hamilton@ThermoFisher.com) Recent advances in ion optics and electronic design have added features to the new range of NobleGas mass spectrometers from Thermo Fisher Scientific that will enable the scientific community to resolve a number of existing analytical limitations. The first development relates to detector technology. Because instrument transmission and ion source efficiency can be very high, detector noise can be the limiting factor for ultra-small sample analysis. Faraday cup detectors are the detectors of choice for high accuracy and high precision isotope ratio measurements because of their unmatched stability and linearity and because of the electronic cross calibration network available to precisely and accurately cross calibrate the multiple Faraday detector channels against each other. Today, most IOMS systems are equipped with current amplifiers using a 1011 Ohm resistor coupled to the feedback loop of a high stability and temperature-stabilized operational amplifier. In this paper we will describe our latest investigations in Faraday cup measurements utilising 1012 & 1013 resistors for signal intensities in the range of 1 pA to 1 fA. The second development relates to a new beam deflection technology added to the ARGUS VI mass spectrometer that enables a fixed collector array to be given some of the properties of a mechanically adjustable array. This enables multidynamic multicollector measurements to be taken utilising a fixed array thus enabling the end user to perform vital detector crosscalibrations “in run”. Lastly we will describe early results on a new high resolution platform and the capabilities of this platform to finally deal with certain isotopic interferences in both the Argon and Neon spectra.

Predominantly carbonaceous HF/HCl-resistant residues from the Allende meteorite are studied. Samples are characterized by SEM/EDXA, X-ray diffraction, INAA, C, S, H, N, and noblegas analyses. Isotopic data for carbon show variations no greater than 5%, while isotopic data from noble gases confirm previously established systematics. Noblegas abundances correlate with those of C and N, and concomitant partial loss of C and normal trapped gas occur during treatments with oxidizing acids. HF/HCl demineralization of bulk meteorite results in similar fractional losses of C and trapped noble gases, which leads to the conclusion that various macromolecular carbonaceous substances serve as the main host phase for normal trapped noble gases and anomalous gases in acid-resistant residues, and as the carrier of the major part of trapped noble gases lost during HF/HCl demineralization. Limits on the possible abundances of dense mineralic host phases in the residues are obtained, and considerations of the nucleogenetic origin for CCF-XE indicate that carbonaceous host phases and various forms of organic matter in carbonaceous meteorites may have a presolar origin.

The components of the physical forces between noblegas atoms, alkali ions, and halogen ions are analyzed and a data base developed from analysis of the two-body potential data, the alkali-halide molecular data, and the noblegas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noblegas atoms on noblegas surfaces and salt crystal surfaces with surface tension neglected. Within this context, the noblegas surface potentials on noblegas and salt crystals are considered to be accurate to within several percent.

In this work we present optimized noblegas-water Lennard-Jones 6-12 pair potentials for each noblegas. Given the significantly different atomic nature of water and the noble gases, the standard Lorentz-Berthelot mixing rules produce inaccurate unlike molecular interactions between these two species. Consequently, we find simulated Henry's coefficients deviate significantly from their experimental counterparts for the investigated thermodynamic range (293-353 K at 1 and 10 atm), due to a poor unlike potential well term (εij). Where εij is too high or low, so too is the strength of the resultant noblegas-water interaction. This observed inadequacy in using the Lorentz-Berthelot mixing rules is countered in this work by scaling εij for helium, neon, argon, and krypton by factors of 0.91, 0.8, 1.1, and 1.05, respectively, to reach a much improved agreement with experimental Henry's coefficients. Due to the highly sensitive nature of the xenon εij term, coupled with the reasonable agreement of the initial values, no scaling factor is applied for this noblegas. These resulting optimized pair potentials also accurately predict partitioning within a CO2-H2O binary phase system as well as diffusion coefficients in ambient water. This further supports the quality of these interaction potentials. Consequently, they can now form a well-grounded basis for the future molecular modeling of multiphase geological systems. PMID:26452070

Argonne National Laboratory (ANL) and the University of Cincinnati (UC) have been developing a new class of ultrasensitive noblegas detectors that are based upon the ANL discovery that corn oil has a high affinity for heavy noblegas absorption at room temperature, but releases the noble gases with warming or by other low-energy-input means. Environmental applications for this new class of fluid-based detectors include ultrahigh sensitivity radioxenon detectors for Comprehensive Test Ban Treaty Surveillance, improved fission gas detectors for enhanced environmental surveillance in the vicinity of DOE, DOD, and NRC-licensed facilities, and improved integrating Rn detectors for earthquake prediction. The purpose of the present paper is to present the results of theoretical and experimental investigations into the solubility phenomena of heavy noble gases (Rn, Xe, and Kr) in triglyceride oils. It is the authors' intention that the findings presented herein may be used to guide future selection, development, and refinement of vegetable and other hydrocarbon oils to bring further enhancements to noblegas detection efficiencies.

We are developing laser-polarized noblegas nuclear magnetic resonance (NMR) as a novel biomedical imaging tool for ground-based and eventually space-based application. This emerging multidisciplinary technology enables high-resolution gas-space magnetic resonance imaging (MRI) (e.g., of lung ventilation) as well as studies of tissue perfusion. In addition, laser-polarized noble gases (He-3 and Xe-129) do not require a large magnetic field for sensitive detection, opening the door to practical MRI at very low magnetic fields with an open, lightweight, and low-power device. We are pursuing two specific aims in this research. The first aim is to develop a low-field (< 0.01 T) instrument for noblegas MRI of humans, and the second aim is to develop functional MRI of the lung using laser-polarized Xe-129 and related techniques.

For viable CCS implementation variables such as CO2 dissolution rates, reactions with the host rock and the extent of groundwater interaction must be accurately constrained. Noble gases play an important role in these systems [e.g. 1,2]. Their application, however, requires accurate Henry's constants within dense CO2-H2O systems. Current interpretations use pure noblegas-H2O partitioning data [3,4] and assume CO2-noblegas interactions are negligible, even at high (>700 kg/m3) CO2 densities [2]. To test this assumption we experimentally determined noblegas CO2-H2O partitioning for the 170-656 kg/m3 CO2 density range; representative of most CCS environments. Contrary to assumption, CO2 density significantly affected noblegas partition coefficients. For helium, increasing CO2 density resulted in a negative deviation trend from CO2-free values whilst for argon, krypton and xenon strong, positive deviations were observed. At 656 kg/m3 these deviations were -35%, 74%, 114% and 321% respectively. This is interpreted as the CO2 phase acting as a polar solvent inducing polarisation in the noble gases. Deviation trends are well defined using a 2nd order polynomial. The effect of a dense CO2 phase can now be incorporated into existing noblegas models. We also present results from a Gibbs-Ensemble Monte Carlo molecular simulation to model partitioning for this binary system. This fundamental technique makes predictions based on the pair-potentials of interaction between the molecules. Here it gives the phase compositions and Henry coefficients for noble gases. With a proven ability in accurately replicating both the CO2-H2O system and low pressure noblegas Henry constants the focus is now on fully optimising the model to match high pressure observations. [1] Gilfillan et al. (2009) Nature 458 614-618 [2] Gilfillan et al. (2008) GCA 72 1174-1198 [3] Crovetto et al. (1982) J.Chem.Phys. 76 1077-1086 [4] Ballentine et al. in Porcelli et al. (eds.) (2002) Rev.Min.Geo. 47 539-614.

Precise measurements by mass spectrometry of dissolved noble gases (He, Ar, Ne, Kr, Xe) in water samples require careful calibration against laboratory standards with known concentrations. Currently, air pipettes are used for day-to-day calibrations, making estimation of overall analytical uncertainties for dissolved noblegas measurements in water difficult. Air equilibrated water (AEW) is often used as a matrix-equivalent laboratory standard for dissolved gases in groundwater, because of the well-known and constant fractions of noble gases in the atmosphere. AEW standards, however, are only useful if the temperature and pressure of the gas-water equilibrium can be controlled and measured precisely (i.e., to better than 0.5%); contamination and partial sample degassing must also be prevented during sampling. Here we present the details of a new custom air-water equilibration system which consists of an insulated 600 liter tank filled with deionized water, held isothermally at a precise target temperature (<0.05 °C) through the use of a heat exchanger. The temperature and total dissolved gas of the water in the tank are monitored continually, as are atmospheric pressure and air temperature in the laboratory. Different noblegas concentration standards can be reliably produced by accurately controlling the water temperature of the equilibration system. Equilibration characteristics and reproducibility of this system for production of copper tubes containing known amounts of noble gases will be presented.

Noblegas isotopes are used extensively as tracers inhydrologic and paleoclimatic studies. These applications requireknowledge of the isotopic mass (m) dependence of noblegas diffusioncoefficients in water (D), which has not been measured but is estimatedusing experimental D-values for the major isotopes along with an untestedrelationship from kinetic theory, D prop m-0.5. We applied moleculardynamics methods to determine the mass dependence of D for four noblegases at 298 K, finding that D prop m-beta with beta<0.2, whichrefutes the kinetic theory model underlying all currentapplications.

The physiological effects of various hyperpolarized helium and xenon MRI-compatible breathing protocols were investigated in 17 Sprague-Dawley rats, by continuous monitoring of blood oxygen saturation, heart rate, EKG, temperature and endotracheal pressure. The protocols included alternating breaths of pure noblegas and oxygen, continuous breaths of pure noblegas, breath-holds of pure noblegas for varying durations, and helium breath-holds preceded by two helium rinses. Alternate-breath protocols up to 128 breaths caused a decrease in oxygen saturation level of less than 5% for either helium or xenon, whereas 16 continuous-breaths caused a 31.5% +/- 2.3% decrease in oxygen saturation for helium and a 30.7% +/- 1. 3% decrease for xenon. Breath-hold protocols up to 25 s did not cause the oxygen saturation to fall below 90% for either of the noble gases. Oxygen saturation values below 90% are considered pathological. At 30 s of breath-hold, the blood oxygen saturation dropped precipitously to 82% +/- 0.6% for helium, and to 76.5% +/- 7. 4% for xenon. Breath-holds longer than 10 s preceded by pre-rinses caused oxygen saturation to drop below 90%. These findings demonstrate the need for standardized noblegas inhalation procedures that have been carefully tested, and for continuous physiological monitoring to ensure the safety of the subject. We find short breath-hold and alternate-breath protocols to be safe procedures for use in hyperpolarized noblegas MRI experiments. Copyright 2000 John Wiley & Sons, Ltd.

Noblegas geochemistry has for long attempted to recover isotopic signatures of mantle components through analyses of basalt glass or xenoliths, but this quest has been plagued by the occurrence of a conspicuous air component, which appears to have both the isotopic and elemental composition of air (except for helium). It is classically considered to be air added to samples close to the surface, in a poorly understood process called "contamination", due to the interaction of rocks and melts with air or water on emplacement. Focusing on Mid-Ocean Ridge Basalts (and Ocean Island Basalts), gases are mostly borne by vesicles and a number of puzzling observations can be made: - vesicles appear to be heterogeneous at the scale of a centimeter, as shown by stepwise crushing experiments, some vesicles having air, some having mantle gases, some having mixtures of both, - vesicles appear over-pressured (P > 1 bar) in fresh samples, as shown by highly vesiculous samples such as Popping Rocks, - the air component appears to be borne by the largest vesicles, as it is recovered in the first steps of stepwise crushing analyses, - larger samples seem to have more of the air component than smaller ones, - in Popping Rocks, the air component borne by the largest vesicles is overwhelming, - the isotopic composition of Pb-Sr-Nd in Popping Rocks was interpreted as indicating a recycled component (related to the HIMU and EM1 mantle end-members). The air noblegas component was suggested recently to be not seawater, but modern air located in fractures of the glass, which should have opened on cooling and resealed immediately [1]. This model faces some difficulties, such as keeping pressure high in the vesicles. I suggest another interpretation, namely that a large part of the air noble gases in oceanic basalts is recycled in origin [2]. It would have been carried down into the mantle at subduction zones, even if most (typically 90%) of the air noble gases in the slab returns to the

Acid-resistant residues were prepared by HCl-HF demineralization of three H-type ordinary chondrites: Brownfield 1937 (H3), Dimmitt (H3, 4), and Estacado (H6). These residues were found to contain a large proportion of the planetary-type trapped Ar, Kr, and Xe in the meteorites. The similarity of these acid residues to those from carbonaceous chondrites and LL-type ordinary chondrites suggests that the same phase carries the trapped noble gases in all these diverse meteorite types. Because the H group represents a large fraction of all meteorites, this result indicates that the gas-rich carrier phase is as universal as the trapped noble-gas component itself. When treated with an oxidizing etchant, the acid residues lost almost all their complement of noble gases.

Acid-resistant residues were prepared by HCl-HF demineralization of three H-type ordinary chondrites: Brownfield 1937 (H3), Dimmitt (H3, 4), and Estacado (H6). These residues were found to contain a large proportion of the planetary-type trapped Ar, Kr, and Xe in the meteorites. The similarity of these acid residues to those from carbonaceous chondrites and LL-type ordinary chondrites suggests that the same phase carries the trapped noble gases in all these diverse meteorite types. Because the H group represents a large fraction of all meteorites, this result indicates that the gas-rich carrier phase is as universal as the trapped noble-gas component itself. When treated with an oxidizing etchant, the acid residues lost almost all their complement of noble gases.

Tektites are natural silica-rich glasses and are thought to be produced during meteorite collisions with the Earth, similar to impact glasses. They occur in four geographically restricted areas and can be divided in three subgroups: normal or splash-form tektites, aerodynamically shaped tektites, and Muong Nong-type tektites [1]. Splash-form and aerodynamically shaped tektites are several grams in weight and are generally homogeneous in chemistry. On the other hand, Muong Nong-type tektites are up to several kilograms in weight, are irregular in shape, and show layered structure. They are inhomogeneous in chemistry and are enriched in volatile elements such as halogens, boron, zinc, etc., compared to splash-form tektites [1]. Muong Nong-type tektites have larger vesicles than splash-form and aerodynamically shaped tektites. This shows that Muong Nong-type tektites are different from splash-form and aerodynamically shaped tektites in several aspects. We measured noblegas compositions in splash-form tektites [2] and impact glasses [3,4]. Although Ne concentrations in tektites and impact glasses were similar to each other, heavy noblegas (Ar, Kr, and Xe) concentrations in tektites were about 2 orders of magnitude lower than those in impact glasses. In this study, we studied noblegas compositions in some Muong Nong-type tektites in order to compare them with splash-form tektites. Muong Nong-type tektite samples used in this study originated from Ubon Ratchatani in East Thailand, near the border of Laos. Geochemical studies of the samples were made by Koeberl [5]. We measured noblegas concentrations and Ne and Ar isotopic compositions in four Muong Nong-type tektites using mass spectrometry. Noble gases were extracted by three methods: laser probe, crushing, and stepwise heating. Chipped samples of two Muong Nong-type tektites were used in laser probe analysis. We used 160-380 mg of samples for noblegas analysis by crushing and stepwise-heating methods. Noblegas

Two models for generation of heterogeneous He, Ne and Ar isotopic ratios in Icelandic basalts are evaluated using a mixing model and the observed noblegas elemental ratios in Icelandic basalts,Ocean island Basalt (OIBs) and Mid-Ocean Ridge Basalt (MORBs). Additional information is contained in the original extended abstract.

Noble-gas chemistry has been undergoing a renaissance in recent years, due in large part to noble-gas hydrides, HNgY, where Ng = noble-gas atom and Y = electronegative fragment. These molecules are exceptional because of their relatively weak bonding and large dipole moments, which lead to strongly enhanced effects of the environment, complexation, and reactions. In this Account, we discuss the matrix-isolation synthesis of noble-gas hydrides, their spectroscopic and structural properties, and their stabilities.This family of species was discovered in 1995 and now has 23 members that are prepared in noble-gas matrices (HXeBr, HKrCl, HXeH, HXeOH, HXeO, etc.). The preparations of the first neutral argon molecule, HArF, and halogen-free organic noble-gas molecules (HXeCCH, HXeCC, HKrCCH, etc.) are important highlights of the field. These molecules are formed by the neutral H + Ng + Y channel. The first addition reaction involving HNgY molecules was HXeCC + Xe + H --> HXeCCXeH, and this led to the first hydride with two noble-gas atoms (recently extended by HXeOXeH). The experimental synthesis of HNgY molecules starts with production of H and Y fragments in solid noblegas via the UV photolysis of suitable precursors. The HNgY molecules mainly form upon thermal mobilization of the fragments.One of the unusual properties of these molecules is the hindered rotation of some HNgY molecules in solid matrices; this has been theoretically modeled. HNgY molecules also have unusual solvation effects, and the H-Xe stretching mode shifts to higher frequencies (up to about 150 cm-1) upon interaction with other species.The noble hydrides have a new bonding motif: HNgY molecules can be represented in the form (H-Ng)+Y-, where (H-Ng)+ is mainly covalent, whereas the interaction between (HNg)+ and Y- is predominantly ionic. The HNgY molecules are highly metastable species representing high-energy materials. The decomposition process HNgY --> Ng + HY is always strongly exoergic

We demonstrate that 3 keV ion beams, formed from the common noble gasses, He, Ne, Ar, Kr, and Xe, can controllably "sculpt" nanometer scale pores in silicon nitride films. Single nanometer control of structural dimensions in nanopores can be achieved with all ion species despite a very wide range of sputtering yields and surface energy depositions. Heavy ions shrink pores more efficiently and make thinner pores than lighter ions. The dynamics of nanopore closing is reported for each ion species and the results are fitted to an adatom diffusion model with excellent success. We also present an experimental method for profiling the thickness of the local membrane around the nanopore based on low temperature sputtering and data is presented that provides quantitative measurements of the thickness and its dependence on ion beam species. PMID:21331305

NMR images of laser polarized 3He gas were obtained at 21 G using a simple, homebuilt instrument. At such low fields magnetic resonance imaging (MRI) of thermally polarized samples (e.g., water) is not practical. Low-field noblegas MRI has novel scientific, engineering, and medical applications. Examples include portable systems for diagnosis of lung disease, as well as imaging of voids in porous media and within metallic systems. PMID:11543589

NMR images of laser polarized 3He gas were obtained at 21 G using a simple, homebuilt instrument. At such low fields magnetic resonance imaging (MRI) of thermally polarized samples (e.g., water) is not practical. Low-field noblegas MRI has novel scientific, engineering, and medical applications. Examples include portable systems for diagnosis of lung disease, as well as imaging of voids in porous media and within metallic systems.

Gas shales from three cores of Haynesville-Bossier formation have been analysed simultaneously for carbon, nitrogen and noble gases (He, Ne, Ar, Xe) to constrain their source compositions and identify signatures associated with high gas retention. Ten samples from varying depths of 11785 to 12223 feet from each core, retrieved from their centres, have been combusted from 200-1200°C in incremental steps of 100°C, using 5 - 10 mg of each sample. Typically, Xe is released at 200°C and is largely adsorbed, observed in two of the three cores. The third core lacked any measureable Xe. High 40Ar/36Ar ratio up to 8000, is associated with peak release of nitrogen with distinctive isotopic signature, related to breakdown of clay minerals at 500°C. He and Ne are also mostly released at the same temperature step and predominantly hosted in the pore spaces of the organic matter associated with the clay. He may be produced from the uranium related to the organic matter. The enrichment factors of noble gases defined as (iX/36Ar)sample/(iX/36Ar)air where iX denotes any noblegas isotope, show Ne and Xe enrichment observed commonly in sedimentary rocks including shales (Podosek et al., 1980; Bernatowicz et al., 1984). This can be related to interaction of the shales with circulating fluids and diffusive separation of gases (Torgersen and Kennedy, 1999), implying the possibility of loss of gases from these shales. Interaction with circulating fluids (e.g. crustal fluids) have been further confirmed using 20Ne/N2, 36Ar/N2 and 4He/N2 ratios. Deviations of measured 4He/40Ar* (where 40Ar* represents radiogenic 40Ar after correcting for contribution from atmospheric Ar) from expected values has been used to monitorgas loss by degassing. Bernatowicz, T., Podosek, F.A., Honda, M., Kramer, F.E., 1984. The Atmospheric Inventory of Xenon and Noble Gases in Shales: The Plastic Bag Experiment. Journal of Geophysical Research 89, 4597-4611. Podosek, F.A., Honda, M., Ozima, M., 1980

We investigate fluid transport mechanisms in a shale reservoir using natural noblegas tracers. Noblegas tracing is promising due to sensitivity of transport to: pore structure and sizes; phase partitioning between groundwater and liquid and gaseous hydrocarbons; and deformation from hydraulic fracturing and creation of surface area. A time-series of over thirty wellhead fluid samples were collected from two hydraulically-fractured wells with different oil-to-gas ratios, along with production data (i.e., flowrate and pressure). Tracer and production data sets can be combined to infer production flow regimes, to estimate reservoir transport parameters, and to improve forecasts of production decline. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Light noblegas (He-Ne-Ar) solubility has been experimentally determined in a range of materials with six-member, tetrahedral ring structures: beryl, cordierite, tourmaline, antigorite, muscovite, F-phlogopite, actinolite, and pargasite. Helium solubility in these materials is relatively high, 4 × 10-10 to 3 × 10-7 mol g-1 bar-1, which is ∼100 to 100,000× greater than He solubility in olivine, pyroxene, or spinel. Helium solubility broadly correlates with the topology of ring structures within different minerals. Distinctive He-Ne-Ar solubility patterns are associated with the different ring structure topologies. Combined, these observations suggest ring structures have a strong influence on noblegas solubility in materials and could facilitate the recycling of noble gases, along with other volatiles (i.e., water, chlorine, and fluorine), into the mantle. Measurements of Ne and Ar solubility in antigorite, however, are highly variable and correlated with each other, suggesting multiple factors contribute the solubility of noble gases in serpentine-rich materials.

New work on the counting of noblegas atoms, using lasers for the selective ionization and detectors for counting individual particles (electrons or positive ions) is reported. When positive ions are counted, various kinds of mass analyzers (magnetic, quadrupole, or time-of-flight) can be incorporated to provide A selectivity. It is shown that a variety of interesting and important applications can be made with atom-counting techniques which are both atomic number (Z) and mass number (A) selective.

THE noble-gas elemental and isotopic composition in the Earth is significantly different from that of the present atmosphere, and provides an important clue to the origin and history of the Earth and its atmosphere. Possible candidates for the noble-gas composition of the primordial Earth include a solar-like component, a planetary-like component (as observed in primitive meteorites) and a component similar in composition to the present atmosphere. In an attempt to identify the contributions of such components, we have measured isotope ratios of helium and neon in fresh basaltic glasses dredged from Loihi seamount and the East Rift Zone of Kilauea1-3. We find a systematic enrichment in 20Ne and 21Ne relative to 22Ne, compared with atmospheric neon. The helium and neon isotope signatures observed in our samples can be explained by mixing of solar, present atmospheric, radiogenic and nucleogenic components. These data suggest that the noble-gas isotopic composition of the mantle source of the Hawaiian plume is different from that of the present atmosphere, and that it includes a significant solar-like component. We infer that this component was acquired during the formation of the Earth.

The howardite meteorites consist of approximately 200 polymict breccias of eucrite (basaltic) and diogenite (orthopyroxenitic) material (collectively, the HED group) that originate from the asteroid belt. Infrared reflectance spectroscopy of asteroids and laboratory studies of HEDs have indicated that the asteroid 4-Vesta is the likely parent body, and the partially-demolished south pole may be the source region. Asteroid regolith formation processes may be responsible for a number of observed petrological features including impact melt clasts, reworked clasts and mosaisicm. We have identified such features in a study of 30 howardites and polymict eucrites, and developed a regolith grading scheme based on petrology. However, the true regolithic nature of the howardite suite is not well defined, and previous research has suggested correlations between Ni contents of 300 - 1200 micron / g, a minimal variation in Al2O3 content around 8-9 wt% and the presence of solar wind noble gases are key hallmarks of an ancient regolith on Vesta . Through combined petrological, compositional and noblegas research, we aim to better understand howardite petrological diversity, regolith formation processes on parent asteroids, and to establish what defines a truly "regolithic" howardite. Our research will play an integral part in the interpretation of data gathered by the Dawn mission. Here we report the preliminary results from our noblegas analyses of four howardites: LEW 85313, EET 99408, MET 96500 and PCA 02066. Bulk major element compositional data have been collected, further petrological data for the HED group are reported by our colleagues, whilst trace-element analyses are underway. Our work will investigate the extent of whether previously described Ni, Al2O3 and noblegas characteristics are in fact indicative of a "regolithic" howardite.

Density functional and ab initio molecular dynamics studies are carried out to investigate the stability of noblegas encapsulated cucurbit[6]uril (CB[6]) systems. Interaction energy, dissociation energy and dissociation enthalpy are calculated to understand the efficacy of CB[6] in encapsulating noblegas atoms. CB[6] could encapsulate up to three Ne atoms having dissociation energy (zero-point energy corrected) in the range of 3.4-4.1 kcal/mol, whereas due to larger size, only one Ar or Kr atom encapsulated analogues would be viable. The dissociation energy value for the second Ar atom is only 1.0 kcal/mol. On the other hand, the same for the second Kr is -0.5 kcal/mol, implying the instability of the system. The noblegas dissociation processes are endothermic in nature, which increases gradually along Ne to Kr. Kr encapsulated analogue is found to be viable at room temperature. However, low temperature is needed for Ne and Ar encapsulated analogues. The temperature-pressure phase diagram highlights the region in which association and dissociation processes of Kr@CB[6] would be favorable. At ambient temperature and pressure, CB[6] may be used as an effective noblegas carrier. Wiberg bond indices, noncovalent interaction indices, electron density, and energy decomposition analyses are used to explore the nature of interaction between noblegas atoms and CB[6]. Dispersion interaction is found to be the most important term in the attraction energy. Ne and Ar atoms in one Ng entrapped analogue are found to stay inside the cavity of CB[6] throughout the simulation at 298 K. However, during simulation Ng2 units in Ng2@CB[6] flip toward the open faces of CB[6]. After 1 ps, one Ne atom of Ne3@CB[6] almost reaches the open face keeping other two Ne atoms inside. At lower temperature (77 K), all the Ng atoms in Ngn@CB[6] remain well inside the cavity of CB[6] throughout the simulation time (1 ps). PMID:25989462

The significance of clathrate hydrates lies in their ability to encapsulate a vast range of inert gases. Although the natural abundance of a few noble gases (Kr and Xe) is poor their hydrates are generally abundant. It has already been reported that HF doping enhances the stability of hydrogen hydrates and methane hydrates, which prompted us to perform a model study on helium, neon and argon hydrates with their HF doped analogues. For this purpose 5(12), 5(12)6(8) and their HF doped analogues are taken as the model clathrate hydrates, which are among the building blocks of sI, sII and sH types of clathrate hydrate crystals. We use the dispersion corrected and gradient corrected hybrid density functional theory for the calculation of thermodynamic parameters as well as conceptual density functional theory based reactivity descriptors. The method of the ab initio molecular dynamics (AIMD) simulation is used through atom centered density matrix propagation (ADMP) techniques to envisage the structural behaviour of different noblegas hydrates on a 500 fs timescale. Electron density analysis is carried out to understand the nature of Ng-OH2, Ng-FH and Ng-Ng interactions. The current results noticeably demonstrate that the noblegas (He, Ne, and Ar) encapsulation ability of 5(12), 5(12)6(8) and their HF doped analogues is thermodynamically favourable. PMID:25047071

Calculations for predicting the distribution of the products of spallation reactions between high energy protons and target materials are well developed and are used for design and operational applications in many projects both within DOE and in other arenas. These calculations are based on theory and limited experimental data that verifies rates of production of some spallation products exist. At the Spallation Neutron Source, a helium stream from the mercury target flows through a system to remove radioactivity from this mercury target offgas. The operation of this system offers a window through which the production of noble gases from mercury spallation by protons may be observed. This paper describes studies designed to measure the production rates of twelve noblegas isotopes within the Spallation Neutron Source mercury target.

Neutron detection is a technique essential to homeland security, nuclear reactor instrumentation, neutron diffraction science, oil-well logging, particle physics and radiation safety. The current shortage of helium-3, the neutron absorber used in most gas-filled proportional counters, has created a strong incentive to develop alternate methods of neutron detection. Excimer-based neutron detection (END) provides an alternative with many attractive properties. Like proportional counters, END relies on the conversion of a neutron into energetic charged particles, through an exothermic capture reaction with a neutron absorbing nucleus (10B, 6Li, 3He). As charged particles from these reactions lose energy in a surrounding gas, they cause electron excitation and ionization. Whereas most gas-filled detectors collect ionized charge to form a signal, END depends on the formation of diatomic noble-gas excimers (Ar*2, Kr*2,Xe* 2) . Upon decaying, excimers emit far-ultraviolet (FUV) photons, which may be collected by a photomultiplier tube or other photon detector. This phenomenon provides a means of neutron detection with a number of advantages over traditional methods. This thesis investigates excimer scintillation yield from the heavy noble gases following the boron-neutron capture reaction in 10B thin-film targets. Additionally, the thesis examines noble-gas excimer lifetimes with relationship to gas type and gas pressure. Experimental data were collected both at the National Institute of Standards and Technology (NIST) Center for Neutron Research, and on a newly developed neutron beamline at the Maryland University Training Reactor. The components of the experiment were calibrated at NIST and the University of Maryland, using FUV synchrotron radiation, neutron imaging, and foil activation techniques, among others. Computer modeling was employed to simulate charged-particle transport and excimer photon emission within the experimental apparatus. The observed excimer

In this paper, we describe 220Rn calibration source that was developed for liquid noblegas detectors. The key advantage of this source is that it can provide 212Bi-212 Po consecutive events, which enables us to evaluate the vertex resolution of a detector at low energy by comparing low-energy events of 212Bi and corresponding higher-energy α-rays from 212Po. Since 220Rn is a noblegas, a hot metal getter can be used when introduced using xenon as the carrier gas. In addition, no long-life radioactive isotopes are left behind in the detector after the calibration is complete; this has clear advantage over the use of 222Rn which leaves longlife radioactivity, i.e., 210Pb. Using a small liquid xenon test chamber, we developed a system to introduce 220Rn via the xenon carrier gas; we demonstrated the successful introduction of 6 × 102 220Rn atoms in our test environment.

Silicon photomultipliers (SiPMs) are photosensors widely used for imaging in a variety of high energy and nuclear physics experiments. In noble-gas detectors for double-beta decay and dark matter experiments, SiPMs are attractive photosensors for imaging. However they are insensitive to the VUV scintillation emitted by the noble gases (xenon and argon). This difficulty is overcome in the NEXT experiment by coating the SiPMs with tetraphenyl butadiene (TPB) to convert the VUV light into visible light. TPB requires stringent storage and operational conditions to prevent its degradation by environmental agents. The development of UV sensitive SiPMs is thus of utmost interest for experiments using electroluminescence of noble-gas detectors. It is in particular an important issue for a robust and background free ββ0ν experiment with xenon gas aimed by NEXT. The photon detection efficiency (PDE) of UV-enhanced SiPMs provided by Hamamatsu was determined for light in the range 250-500 nm. The PDE of standard SiPMs of the same model (S10362-33-50C), coated and non-coated with TPB, was also determined for comparison. In the UV range 250-350 nm, the PDE of the standard SiPM is shown to decrease strongly, down to about 3%. The UV-enhanced SiPM without window is shown to have the maximum PDE of 44% at 325 nm and 30% at 250 nm. The PDE of the UV-enhanced SiPM with silicon resin window has a similar trend in the UV range, although it is about 30% lower. The TPB-coated SiPM has shown to have about 6 times higher PDE than the non-coated SiPM in the range 250-315 nm. This is however below the performance of the UV-enhanced prototypes in the same wavelength range. Imaging in noble-gas detectors using UV-enhanced SiPMs is discussed.

Hyperbolic two-phase flow models have shown excellent ability for the resolution of a wide range of applications ranging from interfacial flows to fluid mixtures with several velocities. These models account for waves propagation (acoustic and convective) and consist in hyperbolic systems of partial differential equations. In this context, each phase is compressible and needs an appropriate convex equation of state (EOS). The EOS must be simple enough for intensive computations as well as boundary conditions treatment. It must also be accurate, this being challenging with respect to simplicity. In the present approach, each fluid is governed by a novel EOS named "Noble Abel stiffened gas," this formulation being a significant improvement of the popular "Stiffened Gas (SG)" EOS. It is a combination of the so-called "Noble-Abel" and "stiffened gas" equations of state that adds repulsive effects to the SG formulation. The determination of the various thermodynamic functions and associated coefficients is the aim of this article. We first use thermodynamic considerations to determine the different state functions such as the specific internal energy, enthalpy, and entropy. Then we propose to determine the associated coefficients for a liquid in the presence of its vapor. The EOS parameters are determined from experimental saturation curves. Some examples of liquid-vapor fluids are examined and associated parameters are computed with the help of the present method. Comparisons between analytical and experimental saturation curves show very good agreement for wide ranges of temperature for both liquid and vapor.

Magnetic resonance imaging of externally polarized noble gases such as ^3He has been used for pulmonary imaging for more than a decade. Because gas diffusion is impeded by the alveoli, the diffusion coefficient of gas in the lung, measured on a time scale of milliseconds, is reduced compared to that of the same gas mixture in the absence of restrictions. When the alveolar walls decay, as in emphysema, diffusivity in the lung increases. In this paper, the relationship between diffusion measurements and the size of the restricting structures will be discussed. The simple case of diffusion in an impermeable cylinder, a structure similar to the upper respiratory airways in mammals, has been studied. A procedure will be presented by which airways of order 2 mm in diameter may be accurately measured; demonstration experiments with plastic tubes will also be presented. The additional developments needed before this technique becomes practical will be briefly discussed.

Increasing attempts at using gas which leads to hydrate formation as a preservative tool in fresh-cut fruits and vegetables have been reported. In this study, changes in some physical and biochemical properties of fresh-cut green peppers under compressed noblegas treatments were examined. Mixed argonkrypton and argon treatments were performed before cold storage at 5°C for 15 days. Mass loss and cell membrane permeability were found to be the lowest in mixed argon-krypton samples. Besides, a lower CO2 concentration and vitamin C loss were detected in gastreated samples compared to untreated samples (control). While the total phenol degradation was moderately reduced, the effect of the treatment on polyphenoloxidase activity was better at the beginning of the storage period. The minimum changes in quality observed in cut peppers resulted from both mixed and gas treatment alone.

Methods for detecting imminent disruptions and mitigating disruption effects using massive injection of noble gases (He, Ne, or Ar) have been demonstrated on the DIII-D tokamak [1]. A jet of high injected gas density (> 10{sup 24} m{sup -3}) and pressure (> 20 kPa) penetrates the target plasma at the gas sound speed ({approx}300-500 m/s) and increases the atom/ion content of the plasma by a factor of > 50 in several milliseconds. UV line radiation from the impurity species distributes the plasma energy uniformly on the first wall, reducing the thermal load to the divertor by a factor of 10. Runaway electrons are almost completely eliminated by the large density of free and bound electrons supplied by the gas injection. The small vertical plasma displacement before current quench and high ratio of current decay rate to vertical growth rate result in a 75% reduction in peak halo current amplitude and attendant forces.

OAK A271 DISRUPTION MITIGATION WITH HIGH-PRESSURE NOBLEGAS INJECTION. High-pressure gas jets of neon and argon are used to mitigate the three principal damaging effects of tokamak disruptions: thermal loading of the divertor surfaces, vessel stress from poloidal halo currents and the buildup and loss of relativistic electrons to the wall. The gas jet penetrates as a neutral species through to the central plasma at its sonic velocity. The injected gas atoms increase up to 500 times the total electron inventory in the plasma volume, resulting in a relatively benign radiative dissipation of >95% of the plasma stored energy. The rapid cooling and the slow movement of the plasma to the wall reduce poloidal halo currents during the current decay. The thermally collapsed plasma is very cold ({approx} 1-2 eV) and the impurity charge distribution can include > 50% fraction neutral species. If a sufficient quantity of gas is injected, the neutrals inhibit runaway electrons. A physical model of radiative cooling is developed and validated against DIII-D experiments. The model shows that gas jet mitigation, including runaway suppression, extrapolates favorably to burning plasmas where disruption damage will be more severe. Initial results of real-time disruption detection triggering gas jet injection for mitigation are shown.

Liquefied noblegas detectors have been used for various applications in recent years for detecting neutrinos, neutrons, photons, and potentially dark matter. The University of Michigan is developing a detector with liquid argon to produce scintillation light and ionization electrons. Our data collection method will allow high-resolution energy measurement and spatial reconstruction of detected particles by using multi-pixel silicon photomultipliers (SiPM) and a cylindrical time projection chamber (TPC) with a multi-wire endplate. We have already designed a liquid argon condenser and purification unit surrounded by an insulating vacuum, constructed circuitry for temperature and pressure sensors, and created software to obtain high-accuracy sensor readouts. The status of detector development will be presented. Funded through the Michigan Memorial Phoenix Project.

In this article, Iranian NobleGas Analyzing System (INGAS) will be introduced. This system is based on beta-gamma coincidence technique and consists of a well-type NaI(Tl) as gamma or X radiation detector and a cylindrical plastic scintillator to detect beta or conversion electron. Standard NIM modules were utilized to detect coincidence events of detectors. Both the beta and gamma detectors were appropriately calibrated. The efficiency curve of gamma detector for volume geometry was obtained by comparing the results of gamma point sources measurements and simulations of GATE V7.0 Monte Carlo code. The performance of detection system was checked by injection of 222Rn and 131mXe gaseous source in the detection cell. The minimum detectable activity of the system for 133Xe is 1.240±0.024 mBq for 24 h measurement time.

We suggest a prominent modification of the outer shell photoionization cross section in noblegas (NG) endohedral atoms NG-C{sub n} under the action of the electron shell of fullerene C{sub n}. This shell leads to two important effects: a strong enhancement of the cross section due to fullerene shell polarization under the action of the incoming electromagnetic wave and to prominent oscillation of this cross section due to the reflection of a photoelectron from the NG by the fullerene shell. Both factors lead to powerful maxima in the outer shell ionization cross sections of NG-C{sub n}, which we call giant endohedral resonances. The oscillator strength reaches a very large value in the atomic scale, 25. We consider atoms of all noble gases except He. The polarization of the fullerene shell is expressed in terms of the total photoabsorption cross section of the fullerene. The photoelectron reflection is taken into account in the framework of the so-called bubble potential, which is a spherical {delta}-type potential. It is assumed in the derivations that the NG is centrally located in the fullerene. It is also assumed, in accordance with the existing experimental data, that the fullerene radius R{sub C} is much larger than the atomic radius r{sub A} and the thickness {delta}{sub C} of the fullerene shell. As was demonstrated recently, these assumptions allow us to represent the NG-C{sub n} photoionization cross section as a product of the NG cross section and two well-defined calculated factors.

The 1993 Non-Proliferation Experiment (NPE) involved detonating 1 kiloton of chemical explosive in a subsurface cavity which also contained bottles of tracer gases (ref 1). That experiment provided an improved understanding of transport processes relevant to the detection of noblegas signals at the surface emanating from a clandestine underground nuclear explosion (UNE). As an alternative to performing large chemical detonations to simulate gas transport from UNEs, we have developed a test bed for subsurface gas transport, sampling and detection studies using a former UNE cavity. The test bed site allows for the opportunity to evaluate pathways to the surface created by the UNE as well as possible transport mechanisms including barometric pumping and cavity pressurization (ref 2). With the test bed we have monitored long-term chemical tracers as well as newly injected tracers. In order to perform high temporal resolution tracer gasmonitoring, we have also developed a Subsurface Gas Smart Sampler (SGSS) which has application during an actual On Site Inspection (OSI) and is available for deployment in OSI field exercises planned for 2014. Deployment of five SGSS at the remote test bed has provided unparalleled detail concerning relationships involving tracer gas transport to the surface, barometric fluctuations and temporal variations in the natural radon concentration. We anticipate that the results of our tracer experiments will continue to support the development of improved noblegas detection technology for both OSI and International Monitoring System applications. 1. C.R. Carrigan et al., 1996, Nature, 382, p. 528. 2. Y. Sun and C.R. Carrigan, 2012, Pure Appl. Geophys., DOI 10.1007/s00024-012-0514-4.

We present results from a first-principles study on the stability of noblegas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-Ih, ice-Ic, ice-II, and C0 interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C0 water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C0 hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems. PMID:26493915

We present results from a first-principles study on the stability of noblegas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-Ih, ice-Ic, ice-II, and C0 interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C0 water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C0 hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.

We present results from a first-principles study on the stability of noblegas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-I{sub h}, ice-I{sub c}, ice-II, and C{sub 0} interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C{sub 0} water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C{sub 0} hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.

An investigation of noblegas entrapment during synthesis of carbonaceous, macromolecular, and kerogen-like substances is presented. High molecular weight organic matter synthesized in aqueous condensation reactions contained little gas, and the composition was consistent with fractionation due to noblegas solubility in water; however, propane soot produced during a modified Miller-Urey experiment in an aritificial gas mixture contained high concentrations of trapped noble gases that displayed strong elemental fractionation from their reservoirs. It is concluded that theses experiemnts show that processes exist for synthesis of carbonaceous carriers that result in high noblegas concentrations and strong elemental fractionation at temperatures well above those required by absorption to achieve similar effects.

Although the naturally occurring atmospheric noble gases He, Ne, Ar, Kr, and Xe possess great potential as tracers for studying gas exchange in living beings, no direct analytical technique exists for simultaneously determining the absolute concentrations of these noble gases in body fluids in vivo. In this study, using human blood as an example, the absolute concentrations of all stable atmospheric noble gases were measured simultaneously by combining and adapting two analytical methods recently developed for geochemical research purposes. The partition coefficients determined between blood and air, and between blood plasma and red blood cells, agree with values from the literature. While the noble-gas concentrations in the plasma agree rather well with the expected solubility equilibrium concentrations for air-saturated water, the red blood cells are characterized by a distinct supersaturation pattern, in which the gas excess increases in proportion to the atomic mass of the noble-gas species, indicating adsorption on to the red blood cells. This study shows that the absolute concentrations of noble gases in body fluids can be easily measured using geochemical techniques that rely only on standard materials and equipment, and for which the underlying concepts are already well established in the field of noble-gas geochemistry. PMID:24811123

Although the naturally occurring atmospheric noble gases He, Ne, Ar, Kr, and Xe possess great potential as tracers for studying gas exchange in living beings, no direct analytical technique exists for simultaneously determining the absolute concentrations of these noble gases in body fluids in vivo. In this study, using human blood as an example, the absolute concentrations of all stable atmospheric noble gases were measured simultaneously by combining and adapting two analytical methods recently developed for geochemical research purposes. The partition coefficients determined between blood and air, and between blood plasma and red blood cells, agree with values from the literature. While the noble-gas concentrations in the plasma agree rather well with the expected solubility equilibrium concentrations for air-saturated water, the red blood cells are characterized by a distinct supersaturation pattern, in which the gas excess increases in proportion to the atomic mass of the noble-gas species, indicating adsorption on to the red blood cells. This study shows that the absolute concentrations of noble gases in body fluids can be easily measured using geochemical techniques that rely only on standard materials and equipment, and for which the underlying concepts are already well established in the field of noble-gas geochemistry. PMID:24811123

Three progressive alteration parameters have been identified from the mineralogical and textural analyses of 7 CM chondritic falls. These indices predict the following order of progressive alteration [3]: Murchison (MC)noble gases, Ar^36, Xe^84, and Kr^132. Two of the progressive alteration parameters monitor the volumetric production of CM phyllosilicates, which was estimated from the modal analysis of 1 to 3 thin sections from each of the analyzed falls. These are the percentages of phyllosilicates in chondrules and the volume of anhydrous matrix silicates, which increase and decease, respectively, with progressive alteration. The third alteration index, the mean Fe^3+/(2-Si) ratio in phyllosilicates, is a stoichiometric-based approximation that monitors variations in mineral composition during progressive alteration, and decreases with increasing alteration. Values of Fe^3+/(2-Si) were calculated from an average of microprobe analyses of matrix phyllosilicates in each meteorite based on a generalized phyllosilicate stoichiometry, [(Fe, Mg)(sub)3-x (Al,Fe^3+)(sub)x(Si(sub)(2-x)(Al,Fe^3+)(sub)x)O(sub)5(OH)(sub)4], which accommodates a continuous transition from cronstedtite to serpentine compositions. The bulk Ar^36 content of the 7 investigated samples decreases with increasing alteration as predicted by the alteration parameters, which suggests the possibility of degassing events. The same trend is observed for Kr^84 and Xe^132. The loss of noble gases in CM chondritic meteorites has previously been noted [1,5], and may be related to the open-system behavior that is predicted for other volatile components in CM chondrites, such as C1 [4], water [3], and methane [2]. Although high-temperature minerals are depleted in noble gases relative to the low

The physical forces between atoms and molecules are important in a number of processes of practical importance, including line broadening in radiative processes, gas and crystal properties, adhesion, and thin films. The components of the physical forces between noblegas atoms, alkali ions, and halogen ions are analyzed and a data base for the dispersion forces is developed from the literature based on evaluations with the harmonic oscillator dispersion model for higher order coefficients. The Zener model of the repulsive core is used in the context of the recent asymptotic wave functions of Handler and Smith; and an effective ionization potential within the Handler and Smith wave functions is defined to analyze the two body potential data of Waldman and Gordon, the alkali-halide molecular data, and the noblegas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noblegas atoms on noblegas and salt crystal surfaces with surface tension neglected. Within this context, the noblegas surface potentials on noblegas and salt crystals are considered to be accurate to within several percent.

Noble-gas isotopes are a well-established technique for providing detailed temperature-time histories of rocks and meteorites. We have established the MSFC NobleGas Research Laboratory (MNGRL) at Marshall Space Flight Center to serve as a NASA investigator facility in the wake of the closure of the JSC laboratory formerly run by Don Bogard. The MNGRL lab was constructed to be able to measure all the noble gases, particularly Ar-Ar and I-Xe radioactive dating to find the formation age of rocks and meteorites, and Ar/Kr/Ne cosmic-ray exposure ages to understand when the meteorites were launched from their parent planets.

Polarized noblegas atom samples suitable for a variety of experiments can be produced by spin exchange with laser optically pumped alkali-metal vapors. Most stable and even radioactive isotopes of He, Ne, Kr, Xe and Rn have been polarized, and the field has been paced, in part by laser developments and study of the atomic collision processes. I will focus on two kinds of application: (1) precision measurement of free precession frequencies to probe fundamental concepts such as CP violation, Local Lorentz Invariance and Linearity in Quantum Mechanics; (2) a polarized {sup 3}He target for electron scattering to extract information on the structure of the neutron. The precision measurement techniques take advantage of long coherence times (measured in hours for {sup 3}He and {sup 21}Ne) and large signal to noise ratios to measure frequency shifts with precision 10{sup -7} Hz in one hour. The polarized {sup 3}He target is used to measure asymmetries in deep inelastic electron scattering which are dominated by the neutron since the proton spins are approximately paired in the ground state of the nucleus. The spin dependent structure function of the neutron is an essential probe of the quark-parton structure of the nucleon. All of these investigations combine fundamental and particle physics motivation with atomic physics and precision measurement techniques in a way that spans many subfields of physics.

We present a model explaining the elemental enrichments in Jupiter's atmosphere, particularly the noble gases Ar, Kr, and Xe. While He, Ne, and O are depleted, seven other elements show similar enrichments (~3 times solar, relative to H). Being volatile, Ar is difficult to fractionate from H2. We argue that external photoevaporation by far-ultraviolet (FUV) radiation from nearby massive stars removed H2, He, and Ne from the solar nebula, but Ar and other species were retained because photoevaporation occurred at large heliocentric distances where temperatures were cold enough (lsim 30 K) to trap them in amorphous water ice. As the solar nebula lost H, it became relatively and uniformly enriched in other species. Our model improves on the similar model of Guillot & Hueso. We recognize that cold temperatures alone do not trap volatiles; continuous water vapor production is also necessary. We demonstrate that FUV fluxes that photoevaporated the disk generated sufficient water vapor in regions gas-phase species in amorphous water ice in solar proportions. We find more efficient chemical fractionation in the outer disk: whereas the model of Guillot & Hueso predicts a factor of three enrichment when only <2% of the disk mass remains, we find the same enrichments when 30% of the disk mass remains. Finally, we predict the presence of ~0.1 M ⊕ of water vapor in the outer solar nebula and protoplanetary disks in H II regions.

We present a model explaining the elemental enrichments in Jupiter's atmosphere, particularly the noble gases Ar, Kr, and Xe. While He, Ne, and O are depleted, seven other elements show similar enrichments (∼3 times solar, relative to H). Being volatile, Ar is difficult to fractionate from H{sub 2}. We argue that external photoevaporation by far-ultraviolet (FUV) radiation from nearby massive stars removed H{sub 2}, He, and Ne from the solar nebula, but Ar and other species were retained because photoevaporation occurred at large heliocentric distances where temperatures were cold enough (≲ 30 K) to trap them in amorphous water ice. As the solar nebula lost H, it became relatively and uniformly enriched in other species. Our model improves on the similar model of Guillot and Hueso. We recognize that cold temperatures alone do not trap volatiles; continuous water vapor production is also necessary. We demonstrate that FUV fluxes that photoevaporated the disk generated sufficient water vapor in regions ≲ 30 K to trap gas-phase species in amorphous water ice in solar proportions. We find more efficient chemical fractionation in the outer disk: whereas the model of Guillot and Hueso predicts a factor of three enrichment when only <2% of the disk mass remains, we find the same enrichments when 30% of the disk mass remains. Finally, we predict the presence of ∼0.1 M {sub ⊕} of water vapor in the outer solar nebula and protoplanetary disks in H II regions.

This report presents efforts to develop the use of in situ naturally-occurring noblegas tracers to evaluate transport mechanisms and deformation in shale hydrocarbon reservoirs. Noble gases are promising as shale reservoir diagnostic tools due to their sensitivity of transport to: shale pore structure; phase partitioning between groundwater, liquid, and gaseous hydrocarbons; and deformation from hydraulic fracturing. Approximately 1.5-year time-series of wellhead fluid samples were collected from two hydraulically-fractured wells. The noblegas compositions and isotopes suggest a strong signature of atmospheric contribution to the noble gases that mix with deep, old reservoir fluids. Complex mixing and transport of fracturing fluid and reservoir fluids occurs during production. Real-time laboratory measurements were performed on triaxially-deforming shale samples to link deformation behavior, transport, and gas tracer signatures. Finally, we present improved methods for production forecasts that borrow statistical strength from production data of nearby wells to reduce uncertainty in the forecasts.

The noble gases, which are chemically inert under normal terrestrial conditions but vary systematically across a wide range of atomic mass and diffusivity, offer a multicomponent approach to investigating gas dynamics in unsaturated soil horizons, including transfer of gas between saturated zones, unsaturated zones, and the atmosphere. To evaluate the degree to which fractionation of noble gases in the presence of an advective–diffusive flux agrees with existing theory, a simple laboratory sand column experiment was conducted. Pure CO2 was injected at the base of the column, providing a series of constant CO2 fluxes through the column. At five fixed sampling depths within the system, samples were collected for CO2 and noblegas analyses, and ambient pressures were measured. Both the advection–diffusion and dusty gas models were used to simulate the behavior of CO2 and noble gases under the experimental conditions, and the simulations were compared with the measured depth-dependent concentration profiles of the gases. Given the relatively high permeability of the sand column (5 ´ 10−11 m2), Knudsen diffusion terms were small, and both the dusty gas model and the advection–diffusion model accurately predicted the concentration profiles of the CO2 and atmospheric noble gases across a range of CO2 flux from ?700 to 10,000 g m−2 d−1. The agreement between predicted and measured gas concentrations demonstrated that, when applied to natural systems, the multi-component capability provided by the noble gases can be exploited to constrain component and total gas fluxes of non-conserved (CO2) and conserved (noblegas) species or attributes of the soil column relevant to gas transport, such as porosity, tortuosity, and gas saturation.

Accurate relative noblegas abundances of mantle-derived melts are required in order to further understand the distribution of noble gases in the mantle and fractionation of noble gases during the melting process. Noblegas relative abundances in the majority of oceanic basalts are highly fractionated, at least in part due to late stage, solubility controlled fractionation. Noblegas concentrations in the volatile phase (≡ noblegas:CO 2 ratio) will vary systematically during solubility controlled degassing of a magma. This contribution models the noblegas concentrations in the volatile phase during degassing at different pressures and vesicularities in order to develop a method for correcting fractionation resulting from magmatic degassing, and thereby estimate the "initial" (pre-degassing) noblegas compositions. Correcting for fractionation during magmatic degassing requires: a) a method for determining the volatile fractionation trajectory during degassing; and b) one well constrained mantle volatile composition with which to "fix" the extrapolation. The trajectory of volatile fractionation can be estimated by sequential crushing of basaltic glasses. Vesicles grow during ascent, therefore large vesicles trap early (less fractionated) volatiles while small vesicles trap late (fractionated) volatiles. Sequential crushing of basaltic glasses releases volatiles from progressively smaller vesicles, thereby allowing the fractionation trajectory resulting from degassing to be determined on individual samples. The production rate of both 21Ne and 4He in the mantle is a function of U concentration only, resulting in a constant 21Ne/ 4He production ratio in the mantle which can be used to "fix" the degassing fractionation trajectory determined by sequential crushing. This correction then allows fractionation of 4He from 40Ar prior to degassing to be assessed. This method is illustrated using multiple crushes of a single basaltic glass from the mid-Atlantic Ridge that

In conjunction with the rise of unconventional oil and gas production, there has been a recent rise in interest in noblegas and carbon isotope changes that can occur during the migration of natural gas. Natural gas geochemistry studies use bulk hydrocarbon composition, carbon isotopes, and noblegas isotopes to determine the migration history of gases from source to reservoir, and to trace fugitive gas leaks from reservoirs to shallow groundwater. We present theoretical and experimental work, which helps to explain trends observed in gas composition in various migration scenarios. Noble gases are used as tracers for subsurface fluid flow due to distinct initial compositions in air-saturated water and natural gases. Numerous field studies have observed enrichments and depletions of noble gases after gas-water interaction. A theoretical two-phase gas displacement model shows that differences in noblegas solubility will cause volatile gas components will become enriched at the front of gas plumes, leaving the surrounding residual water stripped of dissolved gases. Changes in hydrocarbon gas composition are controlled by gas solubility in both formation water and residual oil. In addition to model results, we present results from a series of two-phase flow experiments. These results demonstrate the formation of a noblegas isotope banks ahead of a main CO2 gas plume. Additionally, we show that migrating hydrocarbon gas plumes can sweep biogenic methane from groundwater, significantly altering the isotope ratio of the gas itself. Results from multicomponent, two-phase flow experiments qualitatively agree with the theoretical model, and previous field studies. These experimentally verified models for gas composition changes can be used to aid source identification of subsurface gases.

Paleo-temperature recorded in nature archives is a critical parameter to understand climate change in the past. With advantages of unique inert chemical characteristics and sensitive solubilities with temperature, dissolved noble gases in speleothem inclusion water were recently proposed to retrieve terrestrial temperature history. In order to accurately apply this newly-developed speleothem noblegas temperature (NGT) as a reliable proxy, a fundamental issue about behaviors of noble gases in the karst should be first clarified. In this study, we measured noblegas contents in air and dripping water to evaluate any ratio deviation between noble gases. Cave dripping water samples was collected from three selected caves, Shihua Cave in northern China, Furong Cave in southwestern, and Gyukusen Cave in an island located in the western Pacific. For these caves are characterized by a thorough mixing and long-term storage of waters in a karst aquifer by the absence of seasonal oxygen isotope shifts. Ratios of dripping water noble gases are statistically insignificant from air data. Helium isotopic ratios in the dripping water samples match air value. The results indicate that elemental and isotopic signatures of noble gases from air can be frankly preserved in the epikarst and support the fidelity of NGT techniques.

Some non-Fourier encoding methods such as wavelet and direct encoding use spatially localized bases. The spatial localization feature of these methods enables optimized encoding for improved spatial and temporal resolution during dynamically adaptive MR imaging. These spatially localized bases, however, have inherently reduced image signal-to-noise ratio compared with Fourier or Hadamad encoding for proton imaging. Hyperpolarized noble gases, on the other hand, have quite different MR properties compared to proton, primarily the nonrenewability of the signal. It could be expected, therefore, that the characteristics of image SNR with respect to encoding method will also be very different from hyperpolarized noblegas MRI compared to proton MRI. In this article, hyperpolarized noblegas image SNRs of different encoding methods are compared theoretically using a matrix description of the encoding process. It is shown that image SNR for hyperpolarized noblegas imaging is maximized for any orthonormal encoding method. Methods are then proposed for designing RF pulses to achieve normalized encoding profiles using Fourier, Hadamard, wavelet, and direct encoding methods for hyperpolarized noble gases. Theoretical results are confirmed with hyperpolarized noblegas MRI experiments. Copyright 2001 Academic Press.

Atmospheric noble gases (e.g., 22Ne, 36Ar, 84Kr, 130Xe) in crustal fluids are only sensitive to subsurface physical processes. In particular, depletion of atmospheric noble gases in groundwater due to boiling and steam separation is indicative of the occurrence of a thermal event and can thus be used to trace the thermal history of stable tectonic regions. We present noblegas concentrations of 38 deep brines (~ 0.5-3.6 km) from the Michigan Basin. The atmospheric noblegas component shows a strong depletion pattern with respect to air saturated water. Depletion of lighter gases ( 22Ne and 36Ar) is stronger compared to the heavier ones ( 84Kr and 130Xe). To understand the mechanisms responsible for this overall atmospheric noblegas depletion, phase interaction models were tested. We show that this atmospheric noblegas depletion pattern is best explained by a model involving subsurface boiling and steam separation, and thus, consistent with the occurrence of a past thermal event of mantle origin as previously indicated by both high 4He/heat flux ratios and the presence of primordial mantle He and Ne signatures in the basin. Such a conceptual model is also consistent with the presence of past elevated temperatures in the Michigan Basin (e.g., ~ 80-260 °C) at shallow depths as suggested by previous thermal studies in the basin. We suggest that recent reactivation of the ancient mid-continent rift system underneath the Michigan Basin is likely responsible for the release of both heat and mantle noble gases into the basin via deep-seated faults and fracture zones. Relative enrichment of atmospheric Kr and Xe with respect to Ar is also observed, and is interpreted as reflecting the addition of sedimentary Kr and Xe from associated hydrocarbons, following the hydrothermal event. This study pioneers the use of atmospheric noble gases in subsurface fluids to trace the thermal history of stable tectonic regions.

Ureilites are one of the least understood classes of meteorites; they show signs of being processed, but also appear to be primitive, with abundant carbon and trapped noble gases [1-6]. We have now begun to analyze a number of recently recovered specimens: one from the Saharan desert (Acfer 277) amd five from the Antarctic (LEW 85328, LEW 85440, EET 87720, FRO 90036, and FRO 90054). Analyses of Acfer 277, LEW 85328, and EET 87720 are complete (Table 1). Solar noble gases are present in polymict EET 87720, as shown by the three- isotope plot of Fig. 1. There, in contrast to the bulk data point for Acfer 277, data points for EET 87720 deviate from a mixing line between "typical" spallation Ne (as approximated here by the spallation-dominated 1800 degrees C step for EET 87720) and Ne-U [7] toward higher ^20Ne/^22Ne. A line fitted to the EET 87720 data points passes slightly below Ne-B [8]. The situation is similar for sample F1 from polymict EET 83309 [9], which is shown for comparison. Additional support for the presence of solar gases arises from the abundance of ^4He (~9 x 10^-5 cm^3 STP/g in EET 87720-F1, corrected for spallogenic contributions), which in both cases is far higher than in other ureilite bulk samples [6,10]. Also, in the ratio of spallation-corrected ^4He to trapped ^36Ar, these two polymict ureilites clearly stand out. Helium-4/argon-36 ratios in EET 87720-F1 and EET 83309-F1 are ~20 and ~28 respectively, at least 1 order of magnitude higher than in bulk monomict ureilites and 2 orders of magnitude higher than what appears typical of ureilite diamonds [6]. Nilpena, another polymict ureilite [11], also has a ^4He/^36Ar ratio (2.1 in Nilpena II-1 [7]) higher than all monomict ureilites but one (Dingo Pup Donga), indicating the presence of solar noble gases (in variable contents) as a possible general feature of polymict ureilites, similar to the presence in them of nitrogen with high delta(^15N/^14N) [12]. Monomict LEW 85328 has a very high (^22Ne

The energetics for the interaction of the noblegas atoms with the carbon nanotubes (CNTs) are investigated using an analytical model and density functional theory calculations. Encapsulation of the noblegas atoms, He, Ne, Ar, Kr, and Xe into CNTs of various chiralities is studied in detail using an analytical model, developed earlier by Hill and co-workers. The constrained motion of the noblegas atoms along the axes of the CNTs as well as the off-axis motion are discussed. Analyses of the forces, interaction energies, acceptance and suction energies for the encapsulation enable us to predict the optimal CNTs that can encapsulate each of the noblegas atoms. We find that CNTs of radii 2.98 − 4.20 Å (chiral indices, (5,4), (6,4), (9,1), (6,6), and (9,3)) can efficiently encapsulate the He, Ne, Ar, Kr, and Xe atoms, respectively. Endohedral adsorption of all the noblegas atoms is preferred over exohedral adsorption on various CNTs. The results obtained using the analytical model are subsequently compared with the calculations performed with the dispersion-including density functional theory at the M06 − 2X level using a triple-zeta basis set and good qualitative agreement is found. The analytical model is however found to be computationally cheap as the equations can be numerically programmed and the results obtained in comparatively very less time.

The energetics for the interaction of the noblegas atoms with the carbon nanotubes (CNTs) are investigated using an analytical model and density functional theory calculations. Encapsulation of the noblegas atoms, He, Ne, Ar, Kr, and Xe into CNTs of various chiralities is studied in detail using an analytical model, developed earlier by Hill and co-workers. The constrained motion of the noblegas atoms along the axes of the CNTs as well as the off-axis motion are discussed. Analyses of the forces, interaction energies, acceptance and suction energies for the encapsulation enable us to predict the optimal CNTs that can encapsulate each of the noblegas atoms. We find that CNTs of radii 2.98 - 4.20 Å (chiral indices, (5,4), (6,4), (9,1), (6,6), and (9,3)) can efficiently encapsulate the He, Ne, Ar, Kr, and Xe atoms, respectively. Endohedral adsorption of all the noblegas atoms is preferred over exohedral adsorption on various CNTs. The results obtained using the analytical model are subsequently compared with the calculations performed with the dispersion-including density functional theory at the M06 - 2X level using a triple-zeta basis set and good qualitative agreement is found. The analytical model is however found to be computationally cheap as the equations can be numerically programmed and the results obtained in comparatively very less time.

A provision of the Comprehensive Test Ban Treaty (CTBT) allows on-site inspections (OSIs) of suspect nuclear sites to determine if the occurrence of a detected event is nuclear in origin. For an underground nuclear explosion (UNE), the potential success of an OSI depends significantly on the containment scenario of the alleged event as well as the application of air and soil-gas radionuclide sampling techniques in a manner that takes into account both the suspect site geology and the gas transport physics. UNE scenarios may be broadly divided into categories involving the level of containment. The simplest to detect is a UNE that vents a significant portion of its radionuclide inventory and is readily detectable at distance by the International Monitoring System (IMS). The most well contained subsurface events will only be detectable during an OSI. In such cases, 37 Ar and radioactive xenon cavity gases may reach the surface through either "micro-seepage" or the barometric pumping process and only the careful siting of sampling locations, timing of sampling and application of the most site-appropriate atmospheric and soil-gas capturing methods will result in a confirmatory signal. The OSI noblegas field tests NG09 was recently held in Stupava, Slovakia to consider, in addition to other field sampling and analysis techniques, drilling and subsurface noblegas extraction methods that might be applied during an OSI. One of the experiments focused on challenges to soil-gas sampling near the soil-atmosphere interface. During withdrawal of soil gas from shallow, subsurface sample points, atmospheric dilution of the sample and the potential for introduction of unwanted atmospheric gases were considered. Tests were designed to evaluate surface infiltration and the ability of inflatable well-packers to seal out atmospheric gases during sample acquisition. We discuss these tests along with some model-based predictions regarding infiltration under different near

Apparatus and methods of operation are described for determining, with isotopic selectivity, the number of noblegas atoms in a sample. The analysis is conducted within an evacuated chamber which can be isolated by a valve from a vacuum pumping system capable of producing a pressure of 10.sup.-8 Torr. Provision is made to pass pulses of laser beams through the chamber, these pulses having wavelengths appropriate for the resonance ionization of atoms of the noblegas under analysis. A mass filter within the chamber selects ions of a specific isotope of the noblegas, and means are provided to accelerate these selected ions sufficiently for implantation into a target. Specific types of targets are discussed. An electron measuring device produces a signal relatable to the number of ions implanted into the target and thus to the number of atoms of the selected isotope of the noblegas removed from the gas sample. The measurement can be continued until a substantial fraction, or all, of the atoms in the sample have been counted. Furthermore, additional embodiments of the apparatus are described for bunching the atoms of a noblegas for more rapid analysis, and for changing the target for repetitive cycling of the gas in the chamber. The number of repetitions of the cyclic steps depend upon the concentration of the isotope of interest, the separative efficiency of the mass filter, etc. The cycles are continued until a desired selectivity is achieved. Also described are components and a method of operation for a pre-enrichment operation for use when an introduction of a total sample would elevate the pressure within the chamber to levels in excess of those for operation of the mass filter, specifically a quadrupole mass filter. Specific examples of three noblegas isotope analyses are described.

Microdiamonds isolated from CV3 and ordinary chondrites have been found to differ from those in CM2 meteorites in their N contents and low-temperature Xe-component (Xe-P3), even though the amounts of Xe-HL and the delta ^15N are similar [1,2]. We undertook a simultaneous study of N and noble gases in diamond-rich separates of Murchison (CM2), Efremovka (CV3), and Krymka (LL3.0) meteorites to identify the association of N and noblegas components in them and to characterize possible differences. Gases are extracted by combustion in 3 torr oxygen at low temperatures (up to 700 degrees C) and by pyrolysis at higher temperatures. Murchison: There are two peak releases. About 60-90% of all gases are released in the 550 degrees C step, which is characterized by the presence of Ne-A2, Xe-HL, and delta ^15N = -330 per mil. The second peak at 1200 degrees C gave delta ^15N = -567 per mil and showed a clear admixture of Ne-E and Xe-S (measured 20/22 = 4.2, 21/22 = 0.018, 130/132 = 0.309), indicating the presence of SiC. The low-temperature steps (400 degrees and 450 degrees C) gave Xe-P3 with an admixture of Xe-HL. These results are in agreement with our earlier analysis of another aliquot of Murchison C delta [3]. Efremovka (DE-4): There is a broad release in the 550 degrees C and 600 degrees C steps and a second peak at 1200 degrees C. We estimate that about 60% and 40% respectively of the sample are combusted at the two low- temperature steps. Although the 550 degrees C and 600 degrees C steps have similar gas amounts (except for Xe), other gases show significant differences in their isotopic compositions. The minimum delta ^15N of -290 per mil (600 degrees C) is much heavier than the typical C delta value of -330 per mil [1]. Xenon in both fractions is pure Xe-HL, while Kr is different [86/82 = 1.67 (550 degrees C) and 1.91 (600 degrees C)]. The 1200 degrees C fraction shows the presence of a small admixture of Ne-E, Xe-S, and Kr-S, but the delta ^15N (-127 per mil ) is

The noblegas geochemistry of different types of terrestrial diamond including coated stones, alluvial diamonds, framesites, carbonados and impact diamonds yields a wealth of information on the sources of volatiles responsible for diamond formation. We present an illustrated compilation of published analyses of noble gases in different types of natural diamond. Noble gases in diamond record primary signatures from the mantle indicative of their integrated sources, and, the contribution of different metasomatic agents including subducting fluids and kimberlitic melt sampled during diamond growth. In addition, they show evidence of secondary processes such as resorption. Most data are available for coated stones, which trap abundant volatile-rich microscopic inclusions in their rims. While the coated stones are dominated by Mid-Oceanic-Ridge-Basalt (MORB) type noblegas signatures, the other diamond types contain predominantly crustal and atmospheric components although some mantle gases may be present, the latter indicated in elevated 20Ne/22Ne and/or 129Xe/132Xe ratios relative to atmospheric values. Some alluvial diamonds have very high 3He/4He that may represent the presence of a solar component trapped during their formation, but are just as likely to be the result of cosmogenic 3He implantation during their prolonged residence at the Earth's surface. Oceanic-Island-Basalt (OIB) type noble gases occur in nanometer sized inclusions in metamorphic diamond from Kazakhstan, yet their significance as a fingerprint of mantle processes is not fully understood. Implanted noble gases occur near the outer surfaces of individual crystals, and are generally not a major hindrance for the study of mantle signatures, except for polycrystalline diamond like framesites with small grain size. Some diamonds including the polycrystalline carbonados, are dominated by crustal noble gases with no discernible mantle component evidenced by very low 3He/4He and 20Ne/22Ne ratios, and very

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noblegas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noblegas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noblegas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

Nuclear Magnetic Resonance (NMR) studies with hyperpolarized (hp) noble gases are at an exciting interface between physics, chemistry, materials science and biomedical sciences. This paper intends to provide a brief overview and outlook of magnetic resonance imaging (MRI) with hp noble gases other than hp 3He. A particular focus are the many intriguing experiments with 129Xe, some of which have already matured to useful MRI protocols, while others display high potential for future MRI applications. Quite naturally for MRI applications the major usage so far has been for biomedical research but perspectives for engineering and materials science studies are also provided. In addition, the prospects for surface sensitive contrast with hp 83Kr MRI is discussed. PMID:23290627

The photoionization of atoms of noble gases (Ar, Kr, and Xe) by ultrashort electromagnetic pulses of a corrected Gaussian shape is studied theoretically. Computations are performed in the context of perturbation theory using a simple expression for the total probability of photoionization of an atom by electromagnetic pulses. The features of this process are revealed and analyzed for various ranges of the parameters of the problem.

We studied the dissociation dynamics of noblegas dimer ions in two-color infrared intense laser fields by analyzing their fragment-kinetic-energy-release spectra as a function of the pump-probe delay. Our calculations predict a striking ``delay gap'' in the kinetic-energy-spectra for all noblegas dimers that was so far only measured for the Ar2 dimer. We identify this phenomenon as a frustrated dissociation mechanism. This mechanism requests different pump- and probe-pulse wavelengths and involves the pump pulse to both, singly ionize the neutral dimers and dipole-couple adiabatic states in the dimer ion. Supported by the US NSF and DOE.

The objective of this program is to provide, through isotopic analyses of fluids, fluid inclusions, and rocks and minerals coupled with improved methods for geochemical data analysis, needed information regarding sources of geothermal heat and fluids, the spatial distribution of fluid types, subsurface flow, water-rock reaction paths and rates, and the temporal evolution of geothermal systems. Isotopic studies of geothermal fluids have previously been limited to the light stable isotopes of H, C, and O. However, other isotopic systems such as the noble gases (He, Ne, Ar, Kr and Xe) and reactive elements (e.g. B, N, S, Sr and Pb) are complementary and may even be more important in some geothermal systems. The chemistry and isotopic composition of a fluid moving through the crust will change in space and time in response to varying chemical and physical parameters or by mixing with additional fluids. The chemically inert noble gases often see through these variations, making them excellent tracers for heat and fluid sources. Whereas, the isotopic compositions of reactive elements are useful tools in characterizing water-rock interaction and modeling the movement of fluids through a geothermal reservoir.

The noble gases (He, Ne, Ar, Kr and Xe) and SF6 have recently been used as artificial and inherent tracers of CO2 flow and migration from within[1,2] and from geological reservoirs[3]. However, outstanding questions remain, particularly regarding the flow behaviour of the noble gases compared to CO2. Here we present results from specially constructed experimental equipment, which has been used to determine the factors affecting transport of noble gases relative to CO2 in a porous sandstone. The experimental setup consists of a sample loop that can be loaded with a desired gas mixture. This sample can be released as a pulse into a feeder gas stream through a flow cell. The flow cell consists of a 3.6 cm diameter core, which can be of any length. The sample is surrounded by aluminium foil and treated with epoxy resin inside stainless steel tubing. The flow cell is encased by two purpose designed dispersion end plates. Real-time analysis of the arrival peaks of the gases downstream is recorded using a Quadrupole Mass Spectrometer (QMS). For the experiments, a 0.96 m core of Fell Sandstone was selected to represent a porous media. Noble gases and SF6 pulses were flowed through a CO2 carrier gas at five different pressure gradients (10 - 50 kPa) with arrival profiles measured using the QMS. Surprisingly, peak arrival times of He were slower than the other noble gases at each pressure gradient. The differences in peak arrival times between He and other noble gases increased as pressure decreased and the curve profiles for each noblegas differ significantly. The heavier noble gases (Kr and Xe) along with SF6 show a steeper peak rise at initial appearance, but have a longer duration profile than the He curves. Interestingly, the breakthrough curve profiles for both Kr and Xe were similar to SF6 indicating that Kr and Xe could be substituted for SF6, which is a potent greenhouse gas, in tracing applications. In addition, CO2 pulses were passed through a N2 carrier gas. The

Impurity seeding of noble gases is an effective way of decreasing the heat loads onto the divertor targets in fusion devices. To investigate the effect of noble gases on deuterium retention, tungsten targets have been implanted by different noblegas ions and subsequently exposed to deuterium plasma. Irradiation induced defects and deuterium retention in tungsten targets have been characterized by positron annihilation Doppler broadening and thermal desorption spectroscopy. Similar defect distributions are observed in tungsten irradiated by neon and argon, while it is comparatively low in the case of helium. The influence of helium pre-irradiation on deuterium trapping is found to be small based on the desorption spectrum compared with that of the pristine one. Neon and argon pre-irradiation leads to an enhancement of deuterium trapping during plasma exposure. The influence on deuterium retention is found to be argon > neon > helium when comparing at a similar crystal damage level.

Noble-transition metal (noble=Pt,Au; transition=Co,Ni,Cu) alloy particles with sizes of about 5 nm have been studied by in situ high-energy x-ray diffraction while subjected to oxidizing (O2) and reducing (H2) gas atmospheres at elevated temperatures. The different gas atmospheres do not affect substantially the random alloy, face-centered-cubic structure type of the particles but do affect the way the metal atoms pack together. In an O2 atmosphere, atoms get extra separated from each other, whereas, in an H2 atmosphere, they come closer together. The effect is substantial, amounting to 0.1 Å difference in the first neighbor atomic distances, and concurs with a dramatic change of the particle catalytic properties. It is argued that such reactive gas induced “expansion shrinking” is a common phenomenon that may be employed for the engineering of “smart” nanoparticles responding advantageously to envisaged gas environments.

Noble gasses can make covalent bonds. This has been clearly shown for ArH+ as is evidenced by the observation of this molecule ubiquitously in the interstellar medium. In order to augment the list of potential noblegas molecules, highly-accurate quartic field methods are employed here to analyze the ArNH+ radical cation for the first time. This study is in line with previous examinations of ArOH+, ArH2+, and ArH3+. It is shown here that the Arsbnd N bond strength falls below the Arsbnd O bond energy in ArOH+ but in line with that from ArH2+ indicating that ArNH+ could certainly be synthesized in the lab or, potentially, in nature. In order to aid in the search for this noblegas molecular cation, spectroscopic constants, fundamental vibrational frequencies, absorption intensities, and the center-of-mass dipole moment are provided at high-level in order to augment our understanding of noblegas chemistry.

To study the behavior of noblegas atoms (He, Ne and Ar) in bulk tungsten, new DFT-based potentials for W-He, W-Ne and W-Ar interactions were developed by fitting the results obtained from density functional theory calculations. The new potentials adopt the embedded atom method (EAM) formalism, and the "s-band model" is used to describe the many-body interactions between each of the noblegas atoms and its neighboring W atoms. These potentials reproduce the formation energies of point defects and the migration barriers of single noblegas atoms. The simulations using these potentials successfully predict that the tetrahedral interstitial site is more stable than the octahedral interstitial site for X (= He, Ne or Ar) interstitials. Based on these new potentials, the binding interactions of a single X atom with the Xn and Xn-Vacancy clusters and the diffusion properties of Xn clusters in bulk W were studied using molecular dynamics (MD) simulations. The present results indicate that the binding energies obtained using the new potentials are good in agreement with the results of DFT calculations. The migration energies of the clusters increase with both the increase in the atomic radius of noble gases and the increase in the size of the clusters.

Molecular simulations are used to assess the ability of metal-organic framework (MOF) materials to store and separate noble gases. Specifically, grand canonical Monte Carlo simulation techniques are used to predict noblegas adsorption isotherms at room temperature. Experimental trends of noblegas inflation curves of a Zn-based material (IRMOF-1) are matched by the simulation results. The simulations also predict that IRMOF-1 selectively adsorbs Xe atoms in Xe/Kr and Xe/Ar mixtures at total feed gas pressures of 1 bar (14.7 psia) and 10 bar (147 psia). Finally, simulations of a copper-based MOF (Cu-BTC) predict this material's ability to selectively adsorb Xe and Kr atoms when present in trace amounts in atmospheric air samples. These preliminary results suggest that Cu-BTC may be an ideal candidate for the pre-concentration of noble gases from air samples. Additional simulations and experiments are needed to determine the saturation limit of Cu-BTC for xenon, and whether any krypton atoms would remain in the Cu-BTC pores upon saturation.

The use of noble metals as catalysts for mercury oxidation in flue gas remains an area of active study. To date, field studies have focused on gold and palladium catalysts installed at pilot scale. In this article, we introduce bench-scale experimental results for gold, palladium and platinum catalysts tested in realistic simulated flue gas. Our initial results reveal some intriguing characteristics of catalytic mercury oxidation and provide insight for future research into this potentially important process.

This paper presents a novel extraction device for water and noble gases from speleothem samples for noblegas paleotemperature determination. The "combined vacuum crushing and sieving (CVCS) system" was designed to reduce the atmospheric noblegas contents from air inclusions in speleothem samples by up to 2 orders of magnitude without adsorbing atmospheric noble gases onto the freshly produced grain surfaces, a process that had often hampered noblegas temperature (NGT) determination in the past. We also present the results from first performance tests of the CVCS system processing stalagmite samples grown at a known temperature. This temperature is reliably reproduced by the NGTs derived from Ar, Kr, and Xe extracted from the samples. The CVCS system is, therefore, suitable for routine determinations of accurate NGTs. In combination with stalagmite dating, these NGTs will allow reconstructing past regional temperature evolutions, and also support the interpretation of the often complex stable isotope records preserved in the stalagmites' calcite.

Noblegas isotopic signatures and X-ray and electron diffraction characteristics of Tagish Lake indicate that it is a unique carbonaceous chondrite rich in saponite, Fe-Mg-Ca carbonate, primordial noble gases, and presolar grains. Additional information is contained in the original extended abstract.

We report on three new noble-gas molecules, FKrCN, FXeCN, and FXeNC, prepared in low-temperature Kr and Xe matrices. These molecules are made by UV photolysis of FCN in the matrices and subsequent thermal annealing. The FCN precursor is produced by deposition of the matrix gas containing (FCN){sub 3} through a microwave discharge. The new noble-gas molecules are assigned with the help of quantum chemical calculations at the MP2(full) and CCSD(T) levels of theory. Similar Ar compounds (FArCN and FArNC) as well as FKrNC are not found in these experiments, which is in agreement with the calculated energetics.

Calculation of dynamic polarizabilities and hyperpolarizabilities of ionized species using ab initio methods presents computational and conceptual difficulties, as these ionized species often have open-shell electronic system. We use multi-configurational self-consistent field (MCSCF) method with extended basis sets for calculating dynamic polarizability and second-order hyperpolarizabilities of atomic noble gases and their multiply charged cations in non-resonant regime. The calculations were performed at wavelengths ranging from about 100 nm to the red of the first multi-photon resonance all the way toward the static regime. The results were benchmarked to those of CCSD calculations for ions of even-number charge. The second-order hyperpolarizability coefficients were found to decrease when the electrons are progressively removed from the system. At higher ionization states, these coefficients become less dispersive as a function of wavelength. The values and even the signs of the γ (2) coefficients were found to depend on the spin of the ionic quantum state. Thus, for Ne+3 and Ne+4, in low-spin states (2 Pu, and 1 Sg, respectively) the sign of γ (2) is positive, whereas in high-spin states (4 Su, and 3 Pg) the sign is negative. The calculated hyperpolarizabilities of multiply ionized atoms relate to experiments on very bright high-order harmonic generation in multiply ionized plasmas.

Radioxenon isotopes play a major role in confirming whether or not an underground explosion was nuclear in nature. It is then of key importance to understand the sources of environmental radioxenon to be able to distinguish civil sources from those of a nuclear explosion. Based on several years of measurements, combined with advanced atmospheric transport model results, it was recently shown that the main source of radioxenon observations are strong and regular batch releases from a very limited number of medical isotope production facilities. This paper reviews production processes in different medical isotope facilities during which radioxenon is produced. Radioxenon activity concentrations and isotopic compositions are calculated for six large facilities. The results are compared with calculated signals from nuclear explosions. Further, the outcome is compared and found to be consistent with radioxenon measurements recently performed in and around three of these facilities. Some anomalies in measurements in which (131m)Xe was detected were found and a possible explanation is proposed. It was also calculated that the dose rate of the releases is well below regulatory values. Based on these results, it should be possible to better understand, interpret and verify signals measured in the noblegas measurement systems in the International Monitoring of the Comprehensive Nuclear-Test-Ban Treaty. PMID:20447828

Journal article on the role that radioxenon isotopes play in confirming whether or not an underground explosion was nuclear in nature. Radioxenon isotopes play a major role in confirming whether or not an underground explosion was nuclear in nature. It is then of key importance to understand the sources of environmental radioxenon to be able to distinguish civil sources from those of a nuclear explosion. Based on several years of measurements, combined with advanced atmospheric transport model results, it was recently shown that the main source of radioxenon observations are strong and regular batch releases from a very limited number of medical isotope production facilities. This paper reviews production processes in different medical isotope facilities during which radioxenon is produced. Radioxenon activity concentrations and isotopic compositions are calculated for six large facilities. The results are compared with calculated signals from nuclear explosions. Further, the outcome is compared and found to be consistent with radioxenon measurements recently performed in and around three of these facilities. Some anomalies in measurements in which {sup 131m}Xe was detected were found and a possible explanation is proposed. It was also calculated that the dose rate of the releases is well below regulatory values. Based on these results, it should be possible to better understand, interpret and verify signals measured in the noblegas measurement systems in the International Monitoring of the Comprehensive Nuclear-Test-Ban Treaty.

The mass of hydrocarbons that have migrated through tight-gas-sandstone systems before the permeability reduces to trap the hydrocarbon gases provides critical information in the hydrocarbon potential analysis of a basin. The noblegas content (Ne, Ar, Kr, Xe) of the groundwater has a unique isotopic and elemental composition. As gas migrates through the water column, the groundwater-derived noble gases partition into the hydrocarbon phase. Determination of the noble gases in the produced hydrocarbon phase then provides a record of the type of interaction (simple phase equilibrium or open system Rayleigh fractionation). The tight-gas-sand reservoirs of the Rocky Mountains represent one of the most significant gas resources in the United States. The producing reservoirs are generally developed in low permeability (averaging <0.1mD) Upper Cretaceous fluvial to marginal marine sandstones and commonly form isolated overpressured reservoir bodies encased in even lower permeability muddy sediments. We present noblegas data from producing fields in the Greater Green River Basin, Wyoming; the the Piceance Basin, Colorado; and in the Uinta Basin, Utah. The data is consistent from all three basins. We show how in each basin the noble gases record open system gas migration through a water column at maximum basin burial. The data within an open system model indicates that the gas now in-place represents the last ~10% of hydrocarbon gas to have passed through the water column, most likely prior to permeability closedown.

This work reports on the noblegas inventory of 3 new acapulcoites, 3 brachinites, 2 new eucrites from the Dar al Gani region in Libya, the unique achondrite Dar al Gani (DaG) 896 from the same locality, the new eucrite-like achondrite Northwest Africa (NWA) 011, and the controversial sample Tafassasset. We determined cosmic ray exposure and gas retention ages, evaluated shielding conditions, and discuss the trapped noblegas component of the specimens. All exposure ages are within the known range of stony meteorites and partly confirm previously established age clusters. Shielding conditions vary, suggesting substantial shielding for all 3 brachinites and Tafassasset. We cannot exclude, however, that the Mg-rich composition of brachinites simply simulates heavy shielding. Regarding the trapped component, we found Q-like compositions only for the acapulcoite Thiel Mountains (TIL) 99002. The brachinite Elephant Moraine (EET) 99402 yields a high, subsolar 36Ar/ 132Xe ratio of ~400 along with a slightly elevated 84Kr/132Xe ratio, indicating minor atmospheric contamination. All the other samples, particularly the eucrite DaG 983, are characterized by clearly elevated Ar/Kr/Xe ratios due to significant terrestrial alteration. Tafassasset exhibits noblegas parameters that are different from those of CR chondrites, including a relatively high cosmic ray exposure age, the absence of a solar component, low 132Xe concentrations, a low trapped 36Ar/132Xe ratio of ~30, and a noticeable amount of radiogenic 129Xe. Similar attributes have been observed for some primitive achondrites. These attributes are also consistent with the metamorphic character of the sample. We, therefore, consider Tafassasset's noblegas record to be inconclusive as to its classification (primitive achondrite versus metamorphosed CR chondrite).

Sample preparation, involving physical and chemical methods, is an unavoidable step in geochemical analysis. From a noblegas perspective, the two important effects are loss of sample gas and/or incorporation of air, which are significant sources of analytical artifacts. This article reports on the effects of sample exposure to laboratory air without mechanical influence and during sample grinding. The experiments include pure adsorption on terrestrial analog materials (gibbsite and olivine) and grinding of Martian meteorites. A consistent observation is the presence of an elementally fractionated air component in the samples studied. This is a critical form of terrestrial contamination in meteorites as it often mimics the heavy noblegas signatures of known extra-terrestrial end-members that are the basis of important conclusions about the origin and evolution of a meteorite. Although the effects of such contamination can be minimized by avoiding elaborate sample preparation protocols, caution should be exercised in interpreting the elemental ratios (Ar/Xe, Kr/Xe), especially in the low-temperature step extractions. The experiments can also be transferred to the investigation of Martian meteorites with long terrestrial residence times, and to Mars, where the Mars Science Laboratory mission will be able to measure noblegas signatures in the current atmosphere and in rocks and soils collected on the surface in Gale crater.

The use of nonreactive isotopic tracers coupled to a full thermal-hydrological reservoir simulation allows for an improved method of investigating how reservoir fluids contained within matrix and fractures contribute over time to fluids produced from geothermal systems. A combined field and modeling study has been initiated to evaluate the effects of injection, production, and fracture-matrix interaction on produced noblegas contents and isotopic ratios. Gas samples collected periodically from the Aidlin steam field at The Geysers, California, between 1997 and 2006 have been analyzed for their noblegas compositions, and reveal systematic shifts in abundance and isotopic ratios over time. Because of the low concentrations of helium dissolved in the injection waters, the injectate itself has little impact on the helium isotopic composition of the reservoir fluids over time. However, the injection process may lead to fracturing of reservoir rocks and an increase in diffusion-controlled variations in noblegas compositions, related to gases derived from fluids within the rock matrix.

The electron effects of the presence of boron and noblegas dopants in a model silicon lattice were investigated using a self-consistent charge extended Hueckel program. The extent of electronic interaction of the noblegas with the lattice is given by: Kr greater than Ar greater than Ne. Theoretically, boron diffusion in the presence of neon, argon or krypton was examined using a self-consistent charge extended Hueckel program. The net energy of interaction between boron and neon is strongly repulsive while argon-boron exhibits a region of relative stability; krypton exhibits behavior similar to argon though no region of stability was found for the range of separations used in the calculations. Finally, it is noted, from the relative energy of the topmost filled molecular orbital associated with boron (in an interstitial position), that activation of the boron does not require boron movement but can be accomplished by indirect transitions.

The chemical species in cherts and glass fragments were analyzed using micro Raman spectroscopy in conjunction with measurements of heavy noblegas isotopes to characterize hydrothermally derived sedimentary environments.

Key characteristics of California groundwater systems related to aquifer vulnerability, sustainability, recharge locations and mechanisms, and anthropogenic impact on recharge, are revealed in a spatial geostatistical analysis of the data set of tritium, dissolved noblegas and helium isotope analyses collected for the California State Water Resources Control Board's Groundwater Ambient Monitoring and Assessment (GAMA) and California Aquifer Susceptibility (CAS) programs. Over 4,000 tritium and noblegas analyses are available from wells across California. 25% of the analyzed samples contained less than 1 pCi/L indicating recharge occurred before 1950. The correlation length of tritium concentration is 120 km. Nearly 50% of the wells show a significant component of terrigenic helium. Over 50% of these samples show a terrigenic helium isotope ratio (Rter) that is significantly higher than the radiogenic helium isotope ratio (Rrad = 2×10-8). Rter values of more than three times the atmospheric isotope ratio (Ra = 1.384×10-6) are associated with known faults and volcanic provinces in Northern California. In the Central Valley, Rter varies from radiogenic to 2.25 Ra, complicating 3H/3He dating. The Rter was mapped by kriging, showing a correlation length of less than 50 km. The local predicted Rter was used to separate tritiogenic from atmospheric and terrigenic 3He. Regional groundwater recharge areas, indicated by young groundwater ages, are located in the southern Santa Clara Basin and in the upper LA basin and in the eastern San Joaquin Valley and along unlined canals carrying Colorado River water. Recharge in California is dominated by agricultural return flows, river recharge and managed aquifer recharge rather than precipitation excess. Combined application of noble gases and other groundwater tracers reveal the impact of engineered groundwater recharge and prove invaluable for the study of complex groundwater systems. This work was performed under the

Optical detection of single atoms captured in solid noblegas matrices provides an alternative technique to study rare nuclear reactions relevant to nuclear astrophysics. I will describe the prospects of applying this approach for cross section measurements of the ^22Ne,,),25Mg reaction, which is the crucial neutron source for the weak s process inside of massive stars. Noblegas solids are a promising medium for the capture, detection, and manipulation of atoms and nuclear spins. They provide stable and chemically inert confinement for a wide variety of guest species. Because noblegas solids are transparent at optical wavelengths, the guest atoms can be probed using lasers. We have observed that ytterbium in solid neon exhibits intersystem crossing (ISC) which results in a strong green fluorescence (546 nm) under excitation with blue light (389 nm). Several groups have observed ISC in many other guest-host pairs, notably magnesium in krypton. Because of the large wavelength separation of the excitation light and fluorescence light, optical detection of individual embedded guest atoms is feasible. This work is supported by DOE, Office of Nuclear Physics, under contract DE-AC02-06CH11357.

Discovery of the HArF molecule associated with H-Ar covalent bonding [Nature, 2000, 406, 874-876] has revolutionized the field of noblegas chemistry. In general, this class of noblegas compound involving conventional chemical bonds exists as closed-shell species in a singlet electronic state. For the first time, in a bid to predict neutral noblegas chemical compounds in their triplet electronic state, we have carried out a systematic investigation of xenon inserted FN and FP species by using quantum chemical calculations with density functional theory and various post-Hartree-Fock-based correlated methods, including the multireference configuration interaction technique. The FXeP and FXeN species are predicted to be stable by all the computational methods employed in the present work, such as density functional theory (DFT), second-order Møller-Plesset perturbation theory (MP2), coupled-cluster theory (CCSD(T)), and multireference configuration interaction (MRCI). For the purpose of comparison we have also included the Kr-inserted compounds of FN and FP species. Geometrical parameters, dissociation energies, transition-state barrier heights, atomic charge distributions, vibrational frequency data, and atoms-in-molecules properties clearly indicate that it is possible to experimentally realize the most stable state of FXeP and FXeN molecules, which is triplet in nature, through the matrix isolation technique under cryogenic conditions. PMID:25891838

One of the most fundamental noblegas constraints on early Earth history is derived from isotopic differences in (129)Xe/(130)Xe between various terrestrial materials. The short half life (17 m.y.) of extinct (129I, parent of (129)Xe, means that these differences must have been produced within the first 100 m.y. after terrestrial accretion. The identification of large anomalies in (129)Xe/(130)Xe in mid ocean ridge basalts (MORB), with respect to atmospheric xenon, suggests that the atmosphere and upper mantle have remained separate since that time. This alone is a very strong argument for early catastrophic degassing, which would be consistent with an early fractionation resulting in core formation. However, noblegas isotopic systematics of oceanic basalts show that the mantle cannot necessarily be regarded as a homogeneous system, since there are significant variations in (3)He/(4)He, (40)Ar/(36)Ar, and (129)Xe/(130)Xe. Therefore, the early degassing cannot be considered to have acted on the whole mantle. The specific mechanisms of degassing, in particular the thickness and growth of the early crust, is an important variable in understanding present day noblegas inventories. Another constraint can be obtained from rocks that are thought to be derived from near the lithosphere asthenosphere boundary: ultramafic xenoliths.

The aim of our research is to apply the absolute palaeothermometer provided by dissolved noble gases in water to the reliably dated high-resolution archive of speleothems. Here we report on methods used to extract and quantify water and noble gases from fluid inclusions in speleothems and the first successful derivation of noblegas temperatures (NGTs) from this archive. The water amount was determined manometrically, whereas the low noblegas amounts were measured by mass spectrometry, applying rigorous blank control. Gas was extracted by crushing either in a steel cylinder or in a copper tube with little heating, which both yielded acceptably low blanks. Extraction in the steel cylinder is more efficient as a finer grain size distribution can be achieved. A major problem is the often high contribution of noble gases from air inclusions, masking the temperature information present in the noble gases dissolved in water-filled inclusions. However, NGTs with an uncertainty in the range of 1 °C can be derived from suitable stalagmites with low air/water ratios in the inclusions. Such favourable conditions were found to be present in stalagmites of milky white appearance. Suitable samples were collected from the stalagmites BU-U, BU-1 and a soda straw from the Bunker Cave in North-West Germany. Inverse modeling of measured Ne, Ar, Kr, and Xe concentrations leads to a mean temperature of (2.9 ± 0.7) °C for all BU-U sub-samples with an age between 10 800 and 11 700 years and of (7.1 ± 0.8) °C for a 1300 years old sample from BU-1. Compared to the modern mean annual air temperature at the investigated site of about 9.5 °C, the calculated temperatures appear rather low but not unreasonable, as the ages correspond to comparatively cool periods around the Younger Dryas/Preboreal transition and the Early Middle Ages, respectively. Moreover, the indicated temperature difference of about 4 °C between the early and late Holocene periods is in agreement with expectations.

The development of a technically sound protocol for detecting the subsurface release of noblegas radionuclides is critical to the successful operation of an on site inspection (OSI) under the CTBT and has broad ramifications for all aspects of the OSI regime including the setting of specifications for both sampling and analysis equipment used during an OSI. With NA-24 support, we are investigating a variety of issues and concerns that have significant bearing on policy development and technical guidance regarding the detection of noble gases and the creation of a technically justifiable OSI concept of operation. The work at LLNL focuses on optimizing the ability to capture radioactive noble gases subject to the constraints of possible OSI scenarios. This focus results from recognizing the difficulty of detecting gas releases in geologic environments - a lesson we learned previously from the LLNL Non-Proliferation Experiment (NPE). Evaluation of a number of important noblegas detection issues, potentially affecting OSI policy, has awaited the US re-engagement with the OSI technical community. Thus, there have been numerous issues to address during the past 18 months. Most of our evaluations of a sampling or transport issue necessarily involve computer simulations. This is partly due to the lack of OSI-relevant field data, such as that provided by the NPE, and partly a result of the ability of LLNL computer-based models to test a range of geologic and atmospheric scenarios far beyond what could ever be studied in the field making this approach very highly cost effective. We review some highlights of the transport and sampling issues we have investigated during the past year. We complete the discussion of these issues with a description of a preliminary design for subsurface sampling that is intended to be a practical solution to most if not all the challenges addressed here.

Noble gases in several HF/HCl resistant residues of the CM2 chondrite Murchison were measured by closed-system stepped etching, in order to study the planetary gases in their major carrier 'Q'-an ill-defined minor phase, perhaps merely a set of adsorption sites. Neon, Ar, Kr, Xe, and probably also He in 'Q' of Murchison have the same isotopic and nearly the same elemental abundances as their counterparts in Allende (CV3). The isotopic composition of Ne-Q is consistent with mass-dependent fractionation of either solar wind Ne or Ne from solar energetic particles. Unlike Allende, Murchison during HNO3 attack release, besides Q-gases, large amounts of two other Ne-components, Ne-E and Ne-A3, a third subcomponent of Ne-A. This work confirms that Q-gases of well-defined composition were an important noblegas component in the early solar system an are now found in various classes of meteorites, such as carbonaceous chondrites, ureilites, and ordinary chondrites. Ne-Q may have played a role in the formation of noblegas reservoirs in terrestrial planets.

An unexpected feature of Titan's atmosphere is the strong depletion in primordial noble gases revealed by the Gas Chromatograph Mass Spectrometer aboard the Huygens probe during its descent on 2005 January 14. Although several plausible explanations have already been formulated, no definitive response to this issue has yet been found. Here, we investigate the possible sequestration of these noble gases in the liquid contained in lakes and wet terrains on Titan and the consequences for their atmospheric abundances. Considering the atmosphere and the liquid existing on the soil as a whole system, we compute the abundance of each noblegas relative to nitrogen. To do so, we make the assumption of thermodynamic equilibrium between the liquid and the atmosphere, the abundances of the different constituents being determined via regular solution theory. We find that xenon's atmospheric depletion can be explained by its dissolution at ambient temperature in the liquid presumably present on Titan's soil. In the cases of argon and krypton, we find that the fractions incorporated in the liquid are negligible, implying that an alternative mechanism must be invoked to explain their atmospheric depletion.

An unexpected feature of Titan's atmosphere is the strong depletion in primordial noble gases revealed by the Gas Chromatograph Mass Spectrometer aboard the Huygens probe during its descent on 2005 January 14. Although several plausible explanations have already been formulated, no definitive response to this issue has yet been found. Here, we investigate the possible sequestration of these noble gases in the liquid contained in lakes and wet terrains on Titan and the consequences for their atmospheric abundances. Considering the atmosphere and the liquid existing on the soil as a whole system, we compute the abundance of each noblegas relative to nitrogen. To do so, we make the assumption of thermodynamic equilibrium between the liquid and the atmosphere, the abundances of the different constituents being determined via regular solution theory. We find that xenon's atmospheric depletion can be explained by its dissolution at ambient temperature in the liquid presumably present on Titan's soil. In the cases of argon and krypton, we find that the fractions incorporated in the liquid are negligible, implying that an alternative mechanism must be invoked to explain their atmospheric depletion.

The present invention relates generally to nuclear magnetic resonance (NMR) techniques for both spectroscopy and imaging. More particularly, the present invention relates to methods in which hyperpolarized noble gases (e.g., Xe and He) are used to enhance and improve NMR and MRI. Additionally, the hyperpolarized gas solutions of the invention are useful both in vitro and in vivo to study the dynamics or structure of a system. When used with biological systems, either in vivo or in vitro, it is within the scope of the invention to target the hyperpolarized gas and deliver it to specific regions within the system.

Based on the concentrations of dissolved noble gases in fluid inclusions in speleothems and corals, noblegas temperatures (NGT) might be derived, that would be important climate information [1]. In the case of terrestrial carbonates, it means that the temperature dependency of noble gases in the evolving fluid inclusions is suitable to determine the prevailing temperature. This recognition provides new opportunities for the research of paleoclimate. Additionally, the dissolved noble gases in the fluid inclusions represented in corals could be used to study past sea surface temperatures that are one of the most essential parameter of climate reconstructions. To measure dissolved noble gases in fluid inclusions of a few micro-litres, a noblegas mass spectrometer equipped with an ultra high vacuum preparation line is the most suitable way. The preparation of the carbonate samples is performed in a sample preparation system connected to a static mode VG 5400 noblegas mass spectrometer. As a first step of the sample preparation, one piece of a sample is put into a crusher of the preparation line and then evacuated and heated at night. The crushing of dripstone and coral samples is carried out in a stainless steel pipe with a ferro-magnetic ball at 150 °C temperature, in such a way that the ball is kept on elevating and falling down onto the carbonate sample one hundred times. The aim of the heating is to avoid the water released from the fluid inclusions not to be adsorbed on the surface of the freshly broken carbonate [2]. The water released from the fluid inclusions is frozen into a cold finger, being held at temperature of -70 °C for 15 minutes. In this case, the collection efficiency is better than 99.7 %. Then the cold finger is warmed to 27 °C, and the pressure of the water vapour expanded to the volume of the cold finger is determined by a pressure gauge, which accuracy is better than 0.2 % in the pressure range of 10-2 mbar to 11 mbar. The water vapour

To explore the dynamics and implications of incomplete air-sea equilibration during the formation of abyssal water masses, we simulated noble gases in the Estimating the Circulation & Climate of the Ocean (ECCO) global ocean state estimate. A novel computation approach utilizing a matrix-free Newton-Krylov (MFNK) scheme was applied to quickly compute the periodic seasonal solutions for noblegas tracers. MFNK allows for quick computation of a cyclo-stationary solution for tracers (i.e., a spun-up, repeating seasonal cycle), which would otherwise be computationally infeasible due to the long time scale of dynamic adjustment of the abyssal ocean (1000’s of years). A suite of experiments isolates individual processes, including atmospheric pressure effects, the solubility pump and air-sea bubble fluxes. In addition to these modeled processes, a volumetric contribution of 0.28 ± 0.07% of glacial melt water is required to reconcile deep-water observations in the Weddell Sea. Another primary finding of our work is that the saturation anomaly of heavy noble gases in model simulations is in excess of two-fold more negative than is suggested from Weddell Sea observations. This result suggests that model water masses are insufficiently ventilated prior to subduction and thus there is insufficient communication between atmosphere and ocean at high latitudes. The discrepancy between noblegas observations and ECCO simulations highlights that important inadequacies remain in how we model high-latitude ventilation with large implications for the oceanic uptake and storage of carbon.

Isotopic measurements of both stables isotopes and noble gases give important clues to reconstruct the geological history of hydrocarbons, from their generation to their accumulation. Recent analytical advances in carbon isotopes of natural gases (methane to butane and carbon dioxide) allowed to characterize some of the physico-chemical processes which affect natural gas, instead of using these signatures as simple fingerprinting of origins as it was the case some decades ago. These reconstructions provide important information on both the origins and the dynamic behavior of hydrocarbon fluids in sedimentary basins. Moreover, correlating this methodology with other natural tracers increases the knowledge of hydrocarbon history. Among them, noblegas isotopes may be the new frontier tool, as their chemical inertness allows to use them as precise tracers of sources and of associated physical processes (phases behavior, migration and leakage). Moreover, because some isotopes are produced by natural radioactivity, they act therefore as geological clocks, giving potentially a quantification of the residence times of hydrocarbons in a reservoir. The parameters one would hope to constrain, and which may be used as boundary conditions for basin modeling, are the age and the residence time of the fluids constituting a petroleum system, the quantitative estimate of the distance of migration of the hydrocarbons from the source rock to the reservoir and from the petroleum system to the atmosphere, and the proportion of hydrocarbons lost through leakage from the time of accumulation to the present. Other parameters associated with hydrocarbon accumulations, and more conventionally studied, include the relations between source rocks and accumulated fluids, the possible bacterial contribution through methanogenesis and/or biodegradation, the range of maturity of the fluids, the possible dysmigration of the gas from a liquid through evaporative fractionation, the characterization

Gas desorption measurements have been performed on sputter deposited silicon films. The sputter gas was argon or krypton. Parameters influencing the incorporation process e.g. bias voltage, substrate temperature and arrival rate ratio of silicon and noblegas atoms have been systematically varied. The films, a-Si and c-Si, have been characterised by various techniques for composition and defect analysis. A model has been applied to describe the composition of the growing silicon layer. Underlying mechanisms like gas-gas sputtering have been studied in separate ion implantation experiments. For a-Si concentrations as high as 6% Ar and Kr have been found. An important effect is the injection of self-interstitial atoms caused by the low energy heavy ion bombardment. It causes the layer to grow without large open volume defects.

Gas desorption measurements have been performed on sputter deposited silicon films. The sputter gas was argon or krypton. Parameters influencing the incorporation process e.g. bias voltage, substrate temperature and arrival rate ratio of silicon and noblegas atoms have been systematically varied. The films, a-Si and c-Si, have been characterised by various techniques for composition and defect analysis. A model has been applied to describe the composition of the growing silicon layer. Underlying mechanisms like gas-gas sputtering have been studied in separate ion implantation experiments. For a-Si concentrations as high as 6% Ar and Kr have been found. An important effect is the injection of self-interstitial atoms caused by the low energy heavy ion bombardment. It causes the layer to grow without large open volume defects.

Argon, krypton and xenon have different solubilities in water, meaning their ratios in water are different from those in atmospheric air. This characteristic is used in a novel method to distinguish between ice bodies which originate from the compaction of snow (i.e. buried snow banks, glacial ice) vs. ice which forms from the freezing of groundwater (i.e. pingo ice). Ice which forms from the compaction of snow has gas ratios similar to atmospheric air, while ice which forms from the freezing of liquid water is expected to have gas ratios similar to air-equilibrated water. This analysis has been conducted using a spike dilution noblegas line with gas extraction conducted on-line. Samples were mixed with an aliquot of rare noble gases while being melted, then extracted gases are purified and cryogenically separated. Samples have been analysed from glacial ice, buried snow bank ice, intrusive ice, wedge ice, cave ice and two unknown ice bodies. Ice bodies which have formed from different processes have different gas ratios relative to their formation processes.

In past work, we have examined the multi-Mbar response of cryogenically cooled liquid xenon and liquid krypton measuring their Hugoniots to 8 Mbar. These results were utilized in the development of new EOS models for Xe and Kr to use in high energy density physics applications. The previous work demonstrated the usefulness of integrating high accuracy shock compression experiments with DFT to generate the basis for equation of state (EOS) models. In many physics applications, such as Z-pinch experiments, gas mixtures are used instead. However, we do not have reliable experimental data on these mixtures to provide informed decisions about the EOS models or mixture rules. To improve our understanding of mixtures at extreme conditions, we performed dynamic compression experiments using Sandia's Z - facility on a 70/30 molar ratio Kr/Xe cryogenically cooled liquid mixture. We measured the Hugoniot state and reshock state of the liquid mixture to several Mbar. The experimental data validated the DFT simulations for identical molar ratio mixtures. The combined experimental and DFT results are used to assess the EOS models and test the mixture rules. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Securities Administration under Contract No. DE-AC04-94AL85000.

Recent studies in the Michigan Basin looked at the atmospheric and terrigenic noblegas signatures of deep brines to place constraints on the past thermal history of the basin and to assess the extent of vertical transport processes within this sedimentary system. In this contribution, we present noblegas data of shale gas samples from the Antrim shale formation in the Michigan Basin. The Antrim shale was one of the first economic shale-gas plays in the U.S. and has been actively developed since the 1980's. This study pioneers the use of noble gases in subsurface shale gas in the Michigan Basin to clarify the nature of vertical transport processes within the sedimentary sequence and to assess potential variability of noblegas signatures in shales. Antrim Shale gas samples were analyzed for all stable noble gases (He, Ne, Ar, Kr, Xe) from samples collected at depths between 300 and 500m. Preliminary results show R/Ra values (where R and Ra are the measured and atmospheric 3He/4He ratios, respectively) varying from 0.022 to 0.21. Although most samples fall within typical crustal R/Ra range values (~0.02-0.05), a few samples point to the presence of a mantle He component with higher R/Ra ratios. Samples with higher R/Ra values also display higher 20Ne/22Ne ratios, up to 10.4, and further point to the presence of mantle 20Ne. The presence of crustally produced nucleogenic 21Ne and radiogenic 40Ar is also apparent with 21Ne/22Ne ratios up to 0.033 and 40Ar/36Ar ratios up to 312. The presence of crustally produced 4He, 21Ne and 40Ar is not spatially homogeneous within the Antrim shale. Areas of higher crustal 4He production appear distinct to those of crustally produced 21Ne and 40Ar and are possibly related the presence of different production levels within the shale with varying concentrations of parent elements.

Using a new photochemical model of the Earth's early atmosphere, the relationship between noblegas photoionization and organic photochemistry has been investigated from the Archean eon to the present day. We have found that the enhanced UV emission of the young Sun triggered a peculiar atmospheric chemistry in a CH4-rich early atmosphere that resulted in the increased formation of an organic haze, similar to the preliminary results of a previous study (Ribas et al., 2010). We have investigated the interaction between this haze and noble gases photoionized by the UV light from the younger Sun. Laboratory experiments have shown indeed that ionized xenon trapping into organics (1) is more efficient that other ionized noble gases trapping and (2) results in a significant enrichment of heavy xenon isotopes relative to the light ones (e.g., Frick et al., 1979; Marrocchi et al., 2011). We find moreover preferential photoionization of xenon that peaks at an altitude range comparable to that of the organic haze formation, in contrast to other noble gases. Trapping and fractioning of ionized xenon in the organic haze could therefore have been far more efficient than for other noble gases, and could have been particularly effective throughout the Archean eon, since the UV irradiation flux from the young Sun was expected to be substantially higher than today (Ribas et al., 2010; Claire et al., 2012). Thus we suspect that the unique isotopic fractionation of atmospheric xenon and its elemental depletion in the atmosphere relative to other noble gases, compared to potential cosmochemical components, could have resulted from a preferential incorporation of the heaviest xenon isotopes into organics. A fraction of atmospheric xenon could have been continuously trapped in the forming haze and enriched in its heavy isotopes, while another fraction would have escaped from the atmosphere to space, with, or without isotope selection of the lightest isotopes. The combination of these

The interaction of high intensity 100-ps laser pulses with micron-sized noblegas (argon and krypton) droplets is experimentally investigated via a series of pump-probe experiments monitoring the delay-dependent X-ray and extreme ultraviolet (EUV) emission, and by imaging frequency-doubled probe light scattered from the interaction region. An understanding of the time scales for this interaction is important for optimization of EUV sources for next-generation lithography that utilizes laser-produced plasmas (LPP). Depending on the spectral region of interest, the type of emission, and the droplet characteristics, the effective emission lifetime was found to extend from a few hundred picoseconds to as long as several nanoseconds, in agreement with the expected plasma expansion, EUV excitation, and recombination emission time scales.

We are developing technology for laser-polarized noblegas nuclear magnetic resonance (NMR), with the aim of enabling it as a novel biomedical imaging tool for ground-based and eventually space-based application. This emerging multidisciplinary technology enables high-resolution gas-space magnetic resonance imaging (MRI)-e.g., of lung ventilation, perfusion, and gas-exchange. In addition, laser-polarized noble gases (3He and 1BXe) do not require a large magnetic field for sensitive NMR detection, opening the door to practical MRI with novel, open-access magnet designs at very low magnetic fields (and hence in confined spaces). We are pursuing two specific aims in this technology development program. The first aim is to develop an open-access, low-field (less than 0.01 T) instrument for MRI studies of human gas inhalation as a function of subject orientation, and the second aim is to develop functional imaging of the lung using laser-polarized He-3 and Xe-129.

Application of the (40)Ar-(39)Ar method and noblegas studies to diamonds has increased our understanding of their age relationships to the host kimberlite or lamproite, and of the source and composition of volatile-rich fluids in the upper mantle. The properties of diamond (inert, high mechanical strength and low gas diffusivities) means they are especially useful samples for studying gases trapped deep within the earth (less than 150 km) as they are unlikely to have undergone loss or exchange of entrapped material since formation. Volatile-rich fluids (H2O-CO2) are important agents for metasomatic processes in the upper mantle, and the noble gases and halogens preferentially partition into this phase leading to a strong geochemical coherence between these groups of elements. The abundances of the halogens in the major reservoirs of the Earth shows a marked progression from chlorine, concentrated in the oceans, through to iodine which, through its affinity to organic material, is concentrated mainly in sediments. Abundances in the upper mantle are low. This is particularly true for iodine which is of special interest in view of its potential significance as an indicator of sediment recycling and by way of its link to (129)Xe amomalies in the mantle through the low extinct isotope (129)I. Extensions of the (40)Ar-(39)Ar technique enable measurements of halogens and other elements (K, Ca, Ba, U) by production of noblegas isotopes from these species during neutron irradiation. Samples analyzed in this way include 15 coated stones from an unknown source in Zaire, 3 boarts from the Jwaneng and 1 boart from the Orapa kimberlites, both in Botswana.

Far-ultraviolet scintillation signals have been measured in heavy noble gases (argon, krypton, xenon) following boron-neutron capture ({sup 10}B(n,α){sup 7}Li) in {sup 10}B thin films. The observed scintillation yields are comparable to the yields from some liquid and solid neutron scintillators. At noblegas pressures of 107 kPa, the number of photons produced per neutron absorbed following irradiation of a 1200 nm thick {sup 10}B film was 14 000 for xenon, 11 000 for krypton, and 6000 for argon. The absolute scintillation yields from the experimental configuration were calculated using data from (1) experimental irradiations, (2) thin-film characterizations, (3) photomultiplier tube calibrations, and (4) photon collection modeling. Both the boron films and the photomultiplier tube were characterized at the National Institute of Standards and Technology. Monte Carlo modeling of the reaction cell provided estimates of the photon collection efficiency and the transport behavior of {sup 10}B(n,α){sup 7}Li reaction products escaping the thin films. Scintillation yields increased with gas pressure due to increased ionization and excitation densities of the gases from the {sup 10}B(n,α){sup 7}Li reaction products, increased frequency of three-body, excimer-forming collisions, and reduced photon emission volumes (i.e., larger solid angle) at higher pressures. Yields decreased for thicker {sup 10}B thin films due to higher average energy loss of the {sup 10}B(n,α){sup 7}Li reaction products escaping the films. The relative standard uncertainties in the measurements were determined to lie between 14% and 16%. The observed scintillation signal demonstrates that noblegas excimer scintillation is promising for use in practical neutron detectors.

Far-ultraviolet scintillation signals have been measured in heavy noble gases (argon, krypton, xenon) following boron-neutron capture (10B(n,α)7Li) in 10B thin films. The observed scintillation yields are comparable to the yields from some liquid and solid neutron scintillators. At noblegas pressures of 107 kPa, the number of photons produced per neutron absorbed following irradiation of a 1200 nm thick 10B film was 14 000 for xenon, 11 000 for krypton, and 6000 for argon. The absolute scintillation yields from the experimental configuration were calculated using data from (1) experimental irradiations, (2) thin-film characterizations, (3) photomultiplier tube calibrations, and (4) photon collection modeling. Both the boron films and the photomultiplier tube were characterized at the National Institute of Standards and Technology. Monte Carlo modeling of the reaction cell provided estimates of the photon collection efficiency and the transport behavior of 10B(n,α)7Li reaction products escaping the thin films. Scintillation yields increased with gas pressure due to increased ionization and excitation densities of the gases from the 10B(n,α)7Li reaction products, increased frequency of three-body, excimer-forming collisions, and reduced photon emission volumes (i.e., larger solid angle) at higher pressures. Yields decreased for thicker 10B thin films due to higher average energy loss of the 10B(n,α)7Li reaction products escaping the films. The relative standard uncertainties in the measurements were determined to lie between 14% and 16%. The observed scintillation signal demonstrates that noblegas excimer scintillation is promising for use in practical neutron detectors.

Noblegas residence times of saline groundwaters from the 2516 m deep Outokumpu Deep Drill Hole, located within the Precambrian crystalline bedrock of the Fennoscandian Shield in Finland, are presented. The accumulation of radiogenic (4He, 40Ar) and nucleogenic (21Ne) noblegas isotopes in situ together with the effects of diffusion are considered. Fluid samples were collected from depths between 180 and 2480 m below surface, allowing us to compare the modelled values with the measured concentrations along a vertical depth profile. The results show that while the concentrations in the upper part are likely affected by diffusion, there is no indication of diffusive loss at or below 500 m depth. Furthermore, no mantle derived gases were found unequivocally. Previous studies have shown that distinct vertical variation occurs both in geochemistry and microbial community structuring along the drill hole, indicating stagnant waters with no significant exchange of fluids between different fracture systems or with surface waters. Therefore in situ accumulation is the most plausible model for the determination of noblegas residence times. The results show that the saline groundwaters in Outokumpu are remarkably old, with most of the samples indicating residence times between ∼20 and 50 Ma. Although being first order approximations, the ages of the fluids clearly indicate that their formation must predate more recent events, such as Quaternary glaciations. Isolation within the crust since the Eocene-Miocene epochs has also direct implications to the deep biosphere found at Outokumpu. These ecosystems must have been isolated for a long time and thus very likely rely on energy and carbon sources such as H2 and CO2 from groundwater and adjacent bedrock rather than from the ground surface.

We report on experiments using noblegas beams: Helium, Neon, Argon, Krypton, and Xenon, at energies of 1keV, 3keV, and 5keV to controllably fabricate nanopores in freestanding silicon nitride membranes. Utilizing computer simulations (SRIM and TRIM), and a surface adatom diffusion model to describe the phenomenon of nanopore formation, we evaluate the conditions, specifically the ion energy, responsible for highly controllable fabrication of solid state nanopores. Additionally, we present methods to determine the thickness of the grown film as well as the thickness profile of the nanopore.

CASCADR9 is a desert alluvial soil site-specific noblegas transport and fate model. Input parameters for CASCADR9 are: man-made source term, background concentration of radionuclides, radon half-life, soil porosity, period of barometric pressure wave, amplitude of barometric pressure wave, and effective eddy diffusivity. Using average flux, total flow, and radon concentration at the 40 day mark as output parameters, a sensitivity analysis for CASCADR9 is carried out, under a variety of scenarios. For each scenario, the parameter to which output parameters are most sensitive are identified.

Helium partitioning between olivine, orthopyroxene, clinopyroxene, and spinel and basaltic melt has been experimentally determined under upper mantle melting conditions (up to 20 kbar and 1450 °C). Under the conditions explored, helium partition coefficients are similar in all minerals investigated (KdHe˜10-4), suggesting He is evenly distributed between the minerals of spinel peridotite. This is in contrast to most incompatible elements, which are concentrated in clinopyroxene in spinel peridotite. The studied minerals have different concentrations of point defects, but similar He solubility, providing no evidence for He partitioning onto specific defects sites (e.g. cation vacancies). Upper limits on the partition coefficients for Ne and Ar have also been determined, constraining these elements to be moderately to highly incompatible in olivine at the conditions of spinel peridotite melting (<10-2 and <10-3, respectively). Helium partitioning in peridotite minerals varies little within the range of temperatures, pressures, and mineral compositions explored in this study. Reported partition coefficients, in combination with previous work, suggest that moderate to high degree mantle melting is not an efficient mechanism for increasing (U+Th)/He, (U+Th)/Ne, or K/Ar of the depleted mantle (DMM) through time, and consequently, supports the argument that recycling of oceanic crust is largely responsible for the relatively strong radiogenic noblegas signatures in the depleted mantle. Mantle residues with lowered (U+Th)/He, (U+Th)/Ne, and K/Ar may be produced through large extents of melting, but concentrations of noble gases will be low, unless noblegas solubility in solids deviate from Henry's Law at high fugacity.

The purpose of this noblegas investigation was to evaluate the possibility of measuring noble gases in martian rocks and air by future robotic missions such as the Mars Science Laboratory (MSL). The MSL mission has, as part of its payload, the Sample Analysis at Mars (SAM) instrument, which consists of a pyrolysis oven integrated with a GCMS. The MSL SAM instrument has the capability to measure noblegas compositions of martian rocks and atmosphere. Here we suggest the possibility of K-Ar age dating based on noblegas release of martian rocks by conducting laboratory simulation experiments on terrestrial basalts and martian meteorites. We provide requirements for the SAM instrument to obtain adequate noblegas abundances and compositions within the current SAM instrumental operating conditions, especially, a power limit that prevents heating the furnace above approx.1100 C. In addition, Martian meteorite analyses from NASA-JSC will be used as ground truth to evaluate the feasibility of robotic experiments to constrain the ages of martian surface rocks.

Noblegas and nitrogen compositions in the glassy phase of the EETA 79001 shergottite correspond closely with Viking measurements. This direct evidence for the origin of the SNC meteorites on Mars, and for trapping of an unfractionated sample of Martian atmospheric gases in the 79001 glass, provides a reasonable basis for comparing the Martian and terrestrial atmospheres with more precision than that afforded by the Viking data set. Results are that, with one exception, elemental and isotopic compositions of nonradiogenic Martian noble gases are similar to those in the Earth's atmosphere; relatively small isotopic discrepancies in Kr and perhaps Xe may be attributable to different degrees of mass fractionation of a common parent reservoir. The anomaly is in Ar composition, where Martian Ar-36/AR-38 approx. 4 is strikingly lower than the values near 5.3 that characterize both the Earth and major meteoritic gas carriers. Although a primordial Martian ratio of 5.3 could in principle be altered by some planet specific process (e.g., cosmic ray spallation of surface materials) operating over geologic time, one has not been found that works.

Theoretically determined geometries are reported for the light noblegas ions Ng{sub 2}C{sup 2+}, Ng{sub 2}N{sup 2+}, Ng{sub 2}O{sup 2+}, NgCCNg{sup 2+}, NgCCH{sup +}, NgCN{sup +}, and NgNC{sup +} (Ng = He, Ne, Ar) at the MP2/6-31G(d,p) level of theory. In a few cases, optimizations were carried out at CASSCF/6-31G(d,p). The thermodynamic stability of the Ng compounds is investigated at MP4(SDTQ)/6-311G(2df,2pd) for Ng = He, Ne and at MP4(SDTQ)/6-311G(d,p) for Ng = Ar. The structures and stabilities of the molecules are discussed in terms of donor-acceptor interactions between Ng and the respective fragment cation, by using molecular orbital arguments and utilizing the analysis of the electron density distribution and its associated Laplace field. Generally, there is an increase in Ng,X binding interactions of a noblegas molecule NgX with increasing atomic size of Ng. In some cases the Ne,X stabilization energies are slightly smaller than the corresponding He,X values because of repulsive p-{pi} interactions in the neon compounds. The argon molecules are in all cases significantly stronger bound.

First principles calculations in combination with the nudged elastic band method have been performed in order to determine the mobility properties of various noblegas species (He, Ne, Ar, Kr, and Xe) in silicon, a model semiconducting material. We focussed on single impurity, in interstitial configuration or forming a complex with a mono- or a di-vacancy, since the latter are known to be present and to play a key role in the formation of extended defects like bubbles or platelets. We determined several migration mechanisms and associated activation energies and have discussed these results in relation to available experiments. In particular, conflicting measured values of the migration energy of helium are explained by the present calculations. We also predict that helium diffuses solely as an interstitial, while an opposite behaviour is found for heavier species such as Ar, Kr, and Xe, with the prevailing role of complexes in that case. Finally, our calculations indicate that extended defects evolution by Ostwald ripening is possible for helium and maybe neon, but is rather unlikely for heavier noblegas species.

Phase 1 studies focused on the annealing (transient melting) of silicon and germanium targets with a krypton-fluoride (KrF) excimer laser. A suitable target of a semiconducting material--as a means of storing noblegas atoms--is a key component of a device called the RISTRON for counting isotopes of a noblegas. A means for isotopic selective counting of atoms such as 39Ar for ocean water circulation studies and 81Kr for groundwater and ice-cap dating would be of considerable interest to earth scientists. In the RISTRON, ions are created by resonance ionization of neutral krypton atoms released from one of the targets by pulsed laser melting, and these ions are implanted in a second target after isotopic enrichment. The studies evaluated the space charge or plasma effects created as an undesirable by-product of the annealing of a semiconductor with a pulsed excimer laser. The studies showed that the space charge produced when either silicon or germanium is annealed with a KrF laser can be removed with modest electric fields in less than one microsecond.

Atmospheric noble gases (NGs) were used to investigate biogenic gas dynamics in a shallow unconfined aquifer impacted by a crude oil spill, near Bemidji, MN. Concentrations of 3,4He, 20,22Ne, 36,40Ar, Kr, and Xe were determined for gas- and aqueous-phase samples collected from the vadose and saturated zones, respectively. Systematic elemental fractionation of Ne, Ar, Kr, and Xe with respect to air was observed in both of these hydrogeologic zones. Within the vadose zone, relative ratios of Ne and Ar to Kr and Xe revealed distinct process-related trends when compared to corresponding ratios for air. The degree of NG deviation from atmospheric concentrations generally increased with greater atomic mass (i.e., ΔXe > ΔKr > ΔAr > ΔNe), indicating that Kr and Xe are the most sensitive NG tracers in the vadose zone. Reactive transport modeling of the gas data confirms that elemental fractionation can be explained by mass-dependent variations in diffusive fluxes of NGs opposite to a total pressure gradient established between different biogeochemical process zones. Depletion of atmospheric NGs was also observed within a methanogenic zone of petroleum hydrocarbon degradation located below the water table. Solubility normalized NG abundances followed the order Xe > Kr > Ar > Ne, which is indicative of dissolved NG partitioning into the gas phase in response to bubble formation and possibly ebullition. Observed elemental NG ratios of Ne/Kr, Ne/Xe, Ar/Xe, and Kr/Xe and a modeling analysis provide strong evidence that CH4 generation below the water table caused gas exsolution and possibly ebullition and carbon transfer from groundwater to the vadose zone. These results suggest that noble gases provide sensitive tracers in biologically active unconfined aquifers and can assist in identifying carbon cycling and transfer within the vadose zone, the capillary fringe, and below the water table.

Patagonia, in the Southern Andes, is one of the few locations where interactions between the oceanic and continental lithosphere can be studied due to subduction of an active spreading ridge beneath the continent. In order to characterize the noblegas composition of Patagonian subcontinental lithospheric mantle (SCLM), we present the first noblegas data alongside new lithophile (Sr-Nd-Pb) isotopic data for mantle xenoliths from Pali-Aike Volcanic Field and Gobernador Gregores, Southern Patagonia. Based on noblegas isotopic compositions, Pali-Aike mantle xenoliths represent intrinsic SCLM with higher (U + Th + K)/(3He, 22Ne, 36Ar) ratios than the mid-ocean ridge basalt (MORB) source. This reservoir shows slightly radiogenic helium (3He/4He = 6.84-6.90 RA), coupled with a strongly nucleogenic neon signature (mantle source 21Ne/22Ne = 0.085-0.094). The 40Ar/36Ar ratios vary from a near-atmospheric ratio of 510 up to 17700, with mantle source 40Ar/36Ar between 31100-6800+9400 and 54000-9600+14200. In addition, the 3He/22Ne ratios for the local SCLM endmember, at 12.03 ± 0.15 to 13.66 ± 0.37, are higher than depleted MORBs, at 3He/22Ne = 8.31-9.75. Although asthenospheric mantle upwelling through the Patagonian slab window would result in a MORB-like metasomatism after collision of the South Chile Ridge with the Chile trench ca. 14 Ma, this mantle reservoir could have remained unhomogenized after rapid passage and northward migration of the Chile Triple Junction. The mantle endmember xenon isotopic ratios of Pali-Aike mantle xenoliths, which is first defined for any SCLM-derived samples, show values indistinguishable from the MORB source (129Xe/132Xe =1.0833-0.0053+0.0216 and 136Xe/132Xe =0.3761-0.0034+0.0246). The noblegas component observed in Gobernador Gregores mantle xenoliths is characterized by isotopic compositions in the MORB range in terms of helium (3He/4He = 7.17-7.37 RA), but with slightly nucleogenic neon (mantle source 21Ne/22Ne = 0.065-0.079). We

After almost 150 years of quiescence accompanied by weak fumarolic activity, Turrialba volcano (Costa Rica Central Cordillera) is showing signals of potential reawakening. Since 1996, the degassing has become more intense with the extension of the fumarolic field, the opening of new fractures and the occurrence of phreatic explosions (2010-2013). Here, we present a noblegas isotope investigation of crater fumaroles and of fluid inclusions hosted in olivines and pyroxenes from lavas and scoria erupted in the last 10 ka. The 3He/4He ratio of fluid inclusions from the most mafic eruptive products (SiO2=52.5wt% and MgO=6wt%) varies from 7.86 to 8.07 Ra, while that from andesite lavas varies from 7.03 to 7.18 Ra. The most evolved products (SiO2=63wt% and MgO=3wt%) display the lowest 3He/4He ratio (Rc/Ra=6.5). The He isotope values of the most mafic products are in the range of typical arc volcanoes (7-8 Ra), suggesting that contamination of the mantle wedge below the volcano by crustal He is negligible. On the other hand, the lowest values of 3He/4He ratio measured in the most silicic rocks of the series (dacitic) could be representative of a crustal contamination undergone by magma in the plumbing system of Turrialba. The fumaroles collected in 2007-2011 show an helium isotope composition of 7.50-7.96 Ra, which is well in the range of that measured in fluid inclusions from more mafic and recently erupted rocks. This implies that magma involved in the ongoing unrest phase and feeding the crater fumarolic field has petrological and geochemical features comparable to the basaltic-andesitic rocks analyzed in this study. In addition, long-term monitoring of He isotope composition carried out in the last years at Turrialba displays a progressive increase of 3He/4He ratios, which could be related to the simultaneous unrest testified by the increased seismic activity. We infer that this variation could be related to a refill of the plumbing system by 3He-rich magmas, which

Since the first analyses of C and N isotopes in presolar diamonds with known noblegas isotope composition more than a decade ago [1,2] the investigation of these isotope systems in the diamonds were developed practicallly independently. During this time many interesting details in isotopic systematics of all the elements involved were found and reviewed [3-5]. The main conclusion now reached from a decade of investigation is that presolar diamonds from different meteorites are not identical but appear to consist of several populations [6-8]. Therefore a variety of circumstellar conditions may be involved through a type II supernova model is a good start point in trying to understand diamond synthesis [9]. The evidences from experimental data for all the isotope systems however are still not entirely consistent in the sense that we actually do not know how many carriers the diamonds represent and how the various noblegas carriers are related to those for nitrogen. The finding of a consensus between noblegas and light element analyses would seem to be a vital step so that more detailed nucleosynthesis models may be developed tor the diamond formation. A first point is to answer the question whether HL noble gases and light nitrogen must have been formed at the same astrophysical site. Another important achievement in terms of presolar diamond investigations during the last decade is the purity and number of samples now available. However a well known difficulty is that C, N, and noble gases are never measured all together on the same sample. The purpose of collaboration initiated in this paper is to exploit the availability of good quality samples and to go some way towards overcoming the difficulties of measurement technique incompatibility. We have analyzed three pure diamond samples separated at CalTech from Allende, Orgueil, (henceforth CT samples) and Leoville for N and C isotopic composition by stepped pyrolysis and combustion. The samples preparation and

Pressure disequilibria during rapid valve closures can affect calculated molar quantities for a range of gas abundance measurements (e.g., K-Ar geochronology, (U-Th)/He geochronology, noblegas cosmogenic chronology). Modeling indicates this effect in a system with a 10 L reservoir reaches a bias of 1% before 1000 pipette aliquants have been removed from the system, and a bias of 10% before 10,000 aliquants. Herein we explore the causes and effects of this problem, which is the result of volume changes during valve closure. We also present a solution in the form of an electropneumatic pressure regulator that can precisely control valve motion. This solution reduces the effect to ˜0.3% even after 10,000 aliquants have been removed from a 10 L reservoir.

Vinyl radicals produced by annealing-induced reaction of mobilized hydrogen atoms with acetylene molecules in solid noble-gas matrices (Ar, Kr, and Xe) were characterized by Fourier transform infrared and electron paramagnetic resonance (EPR) spectroscopies. The hydrogen atoms were generated from acetylene by UV photolysis or fast electron irradiation. Two vibrational modes of the vinyl radical ({nu}{sub 7} and {nu}{sub 5}) were assigned in IR absorption studies. The assignment is based on data for various isotopic substitutions (D and {sup 13}C) and confirmed by comparison with the EPR measurements and density-functional theory calculations. The data on the {nu}{sub 7} mode is in agreement with previous experimental and theoretical results whereas the {nu}{sub 5} frequency agrees well with the computational data but conflicts with the gas-phase IR emission results.

In hyperpolarized (HP) noble-gas magnetic resonance imaging, large nuclear spin polarizations, about 100,000 times that ordinarily obtainable at thermal equilibrium, are created in 3He and 129Xe. The enhanced signal that results can be employed in high-resolution MRI studies of void spaces such as in the lungs. In HP gas MRI the signal-to-noise ratio (SNR) depends only weakly on the static magnetic field (B(0)), making very low-field (VLF) MRI possible; indeed, it is possible to contemplate portable MRI using light-weight solenoids or permanent magnets. This article reports the first in vivo VLF MR images of the lungs in humans and in rats, obtained at a field of only 15 millitesla (150 Gauss).

We present results demonstrating neutron detection via a closely spaced converter structure coupled to low pressure noblegas scintillation instrumented by a single photo-multiplier tube (PMT). The converter is dispersed throughout the gas volume using a reticulated vitreous carbon foam coated with boron carbide (B{sub 4}C). A calibrated cold neutron beam is used to measure the neutron detection properties, using a thin film of enriched {sup 10}B as a reference standard. Monte Carlo computations of the ion energy deposition are discussed, including treatment of the foam random network. Results from this study indicate that the foam shadows a significant portion of the scintillation light from the PMT. The high scintillation yield of Xe appears to overcome the light loss, facilitating neutron detection and presenting interesting opportunities for neutron detector design.

We describe a device for performing MRI with laser-polarized noblegas at low magnetic fields (<50 G). The system is robust, portable, inexpensive, and provides gas-phase imaging resolution comparable to that of high field clinical instruments. At 20.6 G, we have imaged laser-polarized (3)He (Larmor frequency of 67 kHz) in both sealed glass cells and excised rat lungs, using approximately 0.1 G/cm gradients to achieve approximately 1 mm(2) resolution. In addition, we measured (3)He T(2)(*) times greater than 100 ms in excised rat lungs, which is roughly 20 times longer than typical values observed at high ( approximately 2 T) fields. We include a discussion of the practical considerations for working at low magnetic fields and conclude with evidence of radiation damping in this system. Copyright 1999 Academic Press.

Nitrogen is one of the major non-hydrocarbon gases found in natural gas reservoirs. The objective of this work was to combine the information available from both noblegas and stable isotope systematics to understand the origin of nitrogen and related gas sources, transport behavior, and mass balance within natural gas reservoirs and sedimentary basin systems. The goals achieved are summarized under the following headings: Noblegas and stable isotopes in nitrogen-rich natural gases; Noble gases in groundwater; and Characterization of magmatic and crustal noblegas input into basin systems. Lists of publications and presentations are included.

Discovery of chemoautotrophic microbial communities at the mid-ocean ridges launched the exploration of the "deep hot biosphere". Recent advances have demonstrated however that chemoautotrophic communities are not restricted to high temperature hydrothermal settings. The discovery that the terrestrial subsurface too hosts chemoautotrophic ecosystems sustained by the products of water-rock reactions - albeit at lower temperatures and slower rates of reaction - has expanded our view of the extent of the planet that is habitable. Compelling questions remain. What are the ultimate limits to life in the Earth's deep subsurface? What are the underlying controls on microbial metabolic activity and biodiversity? The answers to these questions may provide insight into the evolutionary relationship of deep terrestrial microbial communities to marine sediment-hosted and vent-hosted communities, into the origin of life on Earth, and the potential for life on other planets and moons. At more than 2 km below surface, fracture waters accessed via mines in the tectonically quiescent Precambrian Shields of Canada and South Africa are dominated by radiogenic noble gases and crustal-derived carbon sources. Key uncertainties concerning the deep terrestrial biosphere in these settings include the rates and mechanisms of carbon cycling far from the photosphere, and hence the scale and significance of this remote and exotic reservoir of the global biogeochemical cycle. While carbon geochemistry and stable isotopes, as well as molecular microbiology, have facilitated major advances in identifying the geochemical and microbiological processes involved, this presentation will highlight how coupling these techniques with noble gases constrains the timescales for the deep carbon cycle. In particular, the coupling of noblegas tracers with carbon geochemistry provides the key to recognizing that hydrogeologically isolated fracture networks of geochemically distinct groundwaters exert a major

Recent studies suggest that seawater-derived noble gases and halogens are recycled into the deep mantle by the subduction of oceanic crust. To understand the processes controlling the availability of halogens and noble gases for subduction, we determined the noblegas elemental and isotopic ratios and halogen (Cl, Br, I) concentrations in 28 igneous samples from the altered oceanic crust (AOC) from 5 ODP sites in the Eastern and Western Pacific Ocean. Crushing followed by heating experiments enabled determination of noble gases and halogens in fluid inclusions and mineral phases respectively. Except for He and Ar, Ne, Kr and Xe isotopic ratios were all air-like suggesting that primary MORB signatures have been completely overprinted by air and/or seawater interaction. In contrast, 3He/4He ratios obtained by crushing indicate that a mantle helium component is still preserved, and 40Ar/36Ar values are affected by radiogenic decay in the mineral phases. The 130Xe/36Ar and 84Kr/36Ar ratios are respectively up to 15 times and 5 times higher than those of seawater and the highest ratios are found in samples affected by low temperature alteration (shallower than 800-900 m sub-basement). We consider three possible processes: (i) adsorption onto the clays present in the samples; (ii) fluid inclusions with a marine pore fluid composition; and (iii) fractionation of seawater through phase separation caused by boiling. Ninety percent of the Cl, Br and I were released during the heating experiments, showing that halogens are dominantly held in mineral phases prior to subduction. I/Cl ratios vary by 4 orders of magnitude, from 3 × 10-6 to 2 × 10-2. The mean Br/Cl ratio is 30% lower than in MORB and seawater. I/Cl ratios lower than MORB values are attributed to Cl-rich amphibole formation caused by hydrothermal alteration at depths greater than 800-900 m sub-basement together with different extents of I loss during low and high temperature alteration. At shallower depths, I

Transmission electron microscopy has been used for structural and physical characterization of nanoscale inclusions of lead and noble gases in aluminum. When the inclusion sizes approach nanoscale dimensions, many of their properties are seen to deviate from similar properties in bulk and in most cases the deviations will increase as the inclusion sizes decrease. Binary alloys of lead and noble gases with aluminum are characterized by extremely low mutual solubilities and inclusions will, therefore, exist as practically pure components embedded in the aluminum matrix. Furthermore, the thermal vacancy mobility in aluminum at and above room temperature is sufficiently high to accommodate volume strains associated with the inclusions thus leading to virtually strain free crystals. The inclusions grow in parallel cube alignment with the aluminum matrix and have a cuboctahedral shape, which reflects directly the anisotropy of the interfacial energies. Inclusions in grain boundaries can have single crystalline or bicrystalline morphology that can be explained from a generalized Wulff analysis such as the xi-vector construction. The inclusions have been found to display a variety of nanoscale features such as high Laplace pressure, size-dependent superheating during melting, deviations from the Wulff shape displaying magic size effects, a shape dependence of edge energy, and so on. All these effects have been observed and monitored by TEM using conventional imaging conditions and high-resolution conditions in combination with in-situ analysis at elevated temperatures. PMID:15549703

The {sup 4}He, {sup 40}Ar, and {sup 136}Xe content dissolved in the pore water of sedimentary rock samples was measured on samples from borehole cores near the repository for nuclear waste in Morsleben, Germany. Due to the very low permeabilities of the rock formations, conventional groundwater sampling was almost impossible. Hence, the authors developed a new sampling method for noble gases in the pore water of freshly drilled rock cores. This method provides vertical noblegas profiles in high depth resolution, even in impermeable rocks. By application of the new technique quantitative age information of groundwater and pore water have been derived. The authors find palaeowaters from the last glaciation depleted in {delta}D and {delta}{sup 18}O with a {sup 4}He age of about 55 kyr. The high saline pore solutions below are at least 6 Mio years old. This has been concluded from the profiles of radiogenic {sup 4}He and {sup 40}Ar close to diffusion in steady-state and from xenon isotopes produced by spontaneous fission of {sup 238}U in the rocks. A {sup 4}He flux of 2 {center_dot} 10{sup {minus}7} cc STP/cm{sup 2} yr is derived from the profile, which is due to local {sup 4}He production within the investigated sediments.

Underground nuclear tests may be first detected by seismic or air samplers operated by the CTBTO (Comprehensive Nuclear-Test-Ban Treaty Organization). After initial detection of a suspicious event, member nations may call for an On-Site Inspection (OSI) that in part, will sample for localized releases of radioactive noble gases and particles. Although much of the commercially available equipment and methods used for surface and subsurface environmental sampling of gases can be used for an OSI scenario, on-site sampling conditions, required sampling volumes and establishment of background concentrations of noble gases require development of specialized methodologies. To facilitate development of sampling equipment and methodologies that address OSI sampling volume and detection objectives, and to collect information required for model development, a field test site was created at a former underground nuclear explosion site located in welded volcanic tuff. A mixture of SF-6, Xe127 and Ar37 was metered into 4400 m3 of air as it was injected into the top region of the UNE cavity. These tracers were expected to move towards the surface primarily in response to barometric pumping or through delayed cavity pressurization (accelerated transport to minimize source decay time). Sampling approaches compared during the field exercise included sampling at the soil surface, inside surface fractures, and at soil vapor extraction points at depths down to 2 m. Effectiveness of various sampling approaches and the results of tracer gas measurements will be presented.

Hyperpolarized noblegas (HNG) magnetic resonance (MR) imaging is a very promising noninvasive tool for the investigation of animal models of lung disease, particularly to follow longitudinal changes in lung function and anatomy without the accumulated radiation dose associated with x rays. The two most common noble gases for this purpose are H3e (helium 3) and X129e (xenon 129), the latter providing a cost-effective approach for clinical applications. Hyperpolarization is typically achieved using spin-exchange optical pumping techniques resulting in ˜10 000-fold improvement in available magnetization compared to conventional Boltzmann polarizations. This substantial increase in polarization allows high spatial resolution (<1 mm) single-slice images of the lung to be obtained with excellent temporal resolution (<1 s). Complete three-dimensional images of the lungs with 1 mm slice thickness can be obtained within reasonable breath-hold intervals (<20 s). This article provides an overview of the current methods used in HNG MR imaging with an emphasis on ventilation studies in animals. Special MR hardware and software considerations are described in order to use the strong but nonrecoverable magnetization as efficiently as possible and avoid depolarization primarily by molecular oxygen. Several applications of HNG MR imaging are presented, including measurement of gross lung anatomy (e.g., airway diameters), microscopic anatomy (e.g., apparent diffusion coefficient), and a variety of functional parameters including dynamic ventilation, alveolar oxygen partial pressure, and xenon diffusing capacity.

Although hydrocarbon production from unconventional energy resources has increased dramatically in the last decade, total unconventional oil and gas recovery from black shales is still less than 25% and 9% of the totals in place, respectively. Further, the majority of increased hydrocarbon production results from increasing the lengths of laterals, the number of hydraulic fracturing stages, and the volume of consumptive water usage. These strategies all reduce the economic efficiency of hydrocarbon extraction. The poor recovery statistics result from an insufficient understanding of some of the key physical processes in complex, organic-rich, low porosity formations (e.g., phase behavior, fluid-rock interactions, and flow mechanisms at nano-scale confinement and the role of natural fractures and faults as conduits for flow). Noble gases and other hydrocarbon tracers are capably of recording subsurface fluid-rock interactions on a variety of geological scales (micro-, meso-, to macro-scale) and provide analogs for the movement of hydrocarbons in the subsurface. As such geochemical data enrich the input for the numerical modeling of multi-phase (e.g., oil, gas, and brine) fluid flow in highly heterogeneous, low permeability formations Herein we will present a combination of noblegas (He, Ne, Ar, Kr, and Xe abundances and isotope ratios) and molecular and isotopic hydrocarbon data from a geographically and geologically diverse set of unconventional hydrocarbon reservoirs in North America. Specifically, we will include data from the Marcellus, Utica, Barnett, Eagle Ford, formations and the Illinois basin. Our presentation will include geochemical and geological interpretation and our perspective on the first steps toward building an advanced reservoir simulator for tracer transport in multicomponent multiphase compositional flow (presented separately, in Moortgat et al., 2015).

The sub-salt hydrocarbon reservoirs in the deep offshore part of the Atlantic Ocean passive margins are a new key target for frontier oil and gas exploration. Type I source rocks locally rich in TOC (Total Organic Carbon) combined with an important secondary connected porosity of carbonate reservoirs overlain by an impermeable salt layer gives rise to reservoirs with high petroleum potential. However, some target structures have been found to be mainly filled with CO2 rich fluids. δ13C of the CO2 is generally between -9 and -4 permil, compatible with a deep source (metamorphic or mantle). Understanding the origin of the CO2 and the relative timing of its input into reservoir layers in regard to the geodynamic context appears to be a key issue for CO2 risk evaluation. The inertness and ubiquity of noble gases in crustal fluids make them powerful tools to trace the origin and migration of mixed fluids (Ballentine and Burnard 2002). The isotopic signature of He, Ne and Ar and the elemental pattern (He to Xe) of reservoir fluid from pressurized bottom hole samples provide an insight into fluid source influences at each reservoir depth. Three main end-members can be mixed into reservoir fluids (e.g. Gilfillan et al., 2008): atmospheric signature due to aquifer recharge, radiogenic component from organic fluid ± metamorphic influence, and mantle input. Their relative fractionation provides insights into the nature of fluid transport (Burnard et al., 2012)and its relative migration timing. In the studied offshore passive margin reservoirs, from both sides of South Atlantic margin, a strong MORB-like magmatic CO2 influence is clear. Hence, CO2 charge must have occurred during or after lithospheric break-up. CO2 charge(s) history appears to be complex, and in some cases requires several inputs to generate the observed noblegas pattern. Combining the knowledge obtained from noblegas (origin, relative timing, number of charges) with organic geochemical and thermodynamic

Numerical models of whole-mantle convection demonstrate that degassing of the mantle is an inefficient process, resulting in ca. 50% of the (40)Ar being degassed from the mantle system. In this sense the numerical simulations are consistent with the (40)Ar mass balance between the atmosphere and mantle reservoir. These models, however, are unable to preserve the large-scale heterogeneity predicted by models invoking geochemical layering of the mantle system. We show that the three most important noble-gas constraints on the geochemically layered mantle are entirely dependent on the (3)He concentration of the convecting mantle derived from the (3)He flux into the oceans and the average ocean-crust generation rate. A factor of 3.5 increase in the convecting-mantle noble-gas concentration removes all requirements for: a (3)He flux into the upper mantle from a deeper high (3)He source; a boundary in the mantle capable of separating heat from helium; and a substantial deep-mantle reservoir to contain a hidden (40)Ar rich reservoir. We call this model concentration for the convecting mantle the 'zero-paradox' concentration. The time-integrated flux of (3)He into the oceans is a robust observation, but only representative of the ocean-floor activity over the last 1000 years. In contrast, ocean-floor generation occurs over tens of millions of years. We argue that combining these two observations to obtain the (3)He concentration of the mantle beneath mid-ocean ridges is unsound. Other indicators of mantle (3)He concentration suggest that the real value may be at least a factor of two higher. As the zero-paradox concentration is approached, the noble-gas requirement for mantle layering is removed. We further consider the role that recycled material plays in ocean-island-basalt generation and show that a source with high (3)He and (3)He/(4)He must exist within the mantle. Nevertheless, only a small amount of this material is required to generate both the observed ocean

Environmental tracers provide information on groundwater age, recharge conditions, and flow processes which can be helpful for evaluating groundwater sustainability and vulnerability. Dissolved noblegas data have proven particularly useful in mountainous terrain because they can be used to determine recharge elevation. However, tracer-derived recharge elevations have not been utilized as calibration targets for numerical groundwater flow models. Herein, we constrain and calibrate a regional groundwater flow model with noble-gas-derived recharge elevations for the first time. Tritium and noblegas tracer results improved the site conceptual model by identifying a previously uncertain contribution of mountain block recharge from the Coast Mountains to an alluvial coastal aquifer in humid southwestern British Columbia. The revised conceptual model was integrated into a three-dimensional numerical groundwater flow model and calibrated to hydraulic head data in addition to recharge elevations estimated from noblegas recharge temperatures. Recharge elevations proved to be imperative for constraining hydraulic conductivity, recharge location, and bedrock geometry, and thus minimizing model nonuniqueness. Results indicate that 45% of recharge to the aquifer is mountain block recharge. A similar match between measured and modeled heads was achieved in a second numerical model that excludes the mountain block (no mountain block recharge), demonstrating that hydraulic head data alone are incapable of quantifying mountain block recharge. This result has significant implications for understanding and managing source water protection in recharge areas, potential effects of climate change, the overall water budget, and ultimately ensuring groundwater sustainability.

The noble gases are the group of elements - helium, neon, argon, krypton, xenon - in the rightmost column of the periodic table of the elements, those which have "filled" outermost shells of electrons (two for helium, eight for the others). This configuration of electrons results in a neutral atom that has relatively low electron affinity and relatively high ionization energy. In consequence, in most natural circumstances these elements do not form chemical compounds, whence they are called "noble." Similarly, much more so than other elements in most circumstances, they partition strongly into a gas phase (as monatomic gas), so that they are called the "noble gases" (also, "inert gases"). (It should be noted, of course, that there is a sixth noblegas, radon, but all isotopes of radon are radioactive, with maximum half-life a few days, so that radon occurs in nature only because of recent production in the U-Th decay chains. The factors that govern the distribution of radon isotopes are thus quite different from those for the five gases cited. There are interesting stories about radon, but they are very different from those about the first five noble gases, and are thus outside the scope of this chapter.)In the nuclear fires in which the elements are forged, the creation and destruction of a given nuclear species depends on its nuclear properties, not on whether it will have a filled outermost shell when things cool off and nuclei begin to gather electrons. The numerology of nuclear physics is different from that of chemistry, so that in the cosmos at large there is nothing systematically special about the abundances of the noble gases as compared to other elements. We live in a very nonrepresentative part of the cosmos, however. As is discussed elsewhere in this volume, the outstanding generalization about the geo-/cosmochemistry of the terrestrial planets is that at some point thermodynamic conditions dictated phase separation of solids from gases, and that the

Noblegas molecules have not hitherto been detected in space. From spectra obtained with the Herschel Space Observatory, we report the detection of emission in the 617.5- and 1234.6-gigahertz J = 1-0 and 2-1 rotational lines of 36ArH+ at several positions in the Crab Nebula, a supernova remnant known to contain both molecular hydrogen and regions of enhanced ionized argon emission. Argon-36 is believed to have originated from explosive nucleosynthesis in massive stars during core-collapse supernova events. Its detection in the Crab Nebula, the product of such a supernova event, confirms this expectation. The likely excitation mechanism for the observed 36ArH+ emission lines is electron collisions in partially ionized regions with electron densities of a few hundred per centimeter cubed.

Noblegas molecules have not hitherto been detected in space. From spectra obtained with the Herschel Space Observatory, we report the detection of emission in the 617.5- and 1234.6-gigahertz J = 1-0 and 2-1 rotational lines of (36)ArH(+) at several positions in the Crab Nebula, a supernova remnant known to contain both molecular hydrogen and regions of enhanced ionized argon emission. Argon-36 is believed to have originated from explosive nucleosynthesis in massive stars during core-collapse supernova events. Its detection in the Crab Nebula, the product of such a supernova event, confirms this expectation. The likely excitation mechanism for the observed (36)ArH(+) emission lines is electron collisions in partially ionized regions with electron densities of a few hundred per centimeter cubed. PMID:24337290

Infrared absorption spectra of formic acid hydrate clusters (HCOOH)m(H2O)n have been measured in noblegas matrices (Ar and Kr). The concentration dependence of the spectra and the comparison with a previous experimental study on HCOOH(H2O) and HCOOH(H2O)2 [Geoge et al., Spectrochim. Acta, Part A 60 (2004) 3225] led to the identification of large clusters. Density functional theory calculations at the B3LYP-DCP/6-31+G(2d,2p) level were carried out to determine the anharmonic vibrational properties of the clusters, enabling a consistent assignment of the observed vibrational peaks to specific clusters.

The integration of precise geochemical analyses with quantitative engineering modeling into an interactive GIS system allows for a sophisticated and efficient method of reservoir engineering and characterization. Geographic Information Systems (GIS) is utilized as an advanced technique for oil field reservoir analysis by combining field engineering and geological/geochemical spatial datasets with the available systematic modeling and mapping methods to integrate the information into a spatially correlated first-hand approach in defining surface and subsurface characteristics. Three key methods of analysis include: 1) Geostatistical modeling to create a static and volumetric 3-dimensional representation of the geological body, 2) Numerical modeling to develop a dynamic and interactive 2-dimensional model of fluid flow across the reservoir and 3) Noblegas geochemistry to further define the physical conditions, components and history of the geologic system. Results thus far include using engineering algorithms for interpolating electrical well log properties across the field (spontaneous potential, resistivity) yielding a highly accurate and high-resolution 3D model of rock properties. Results so far also include using numerical finite difference methods (crank-nicholson) to solve for equations describing the distribution of pressure across field yielding a 2D simulation model of fluid flow across reservoir. Ongoing noblegas geochemistry results will also include determination of the source, thermal maturity and the extent/style of fluid migration (connectivity, continuity and directionality). Future work will include developing an inverse engineering algorithm to model for permeability, porosity and water saturation.This combination of new and efficient technological and analytical capabilities is geared to provide a better understanding of the field geology and hydrocarbon dynamics system with applications to determine the presence of hydrocarbon pay zones (or

The Antrim Shale was one of the first economic shale gas plays in the U.S. and has been actively produced since the 1980's. While previous studies suggest co-produced water in the Antrim is a mixture of brine from deeper formations and freshwater recharge, the extent of water-gas interactions has yet to be determined. The extent and source of thermogenic methane in the Antrim Shale are also under debate. This study uses stable noble gases' (He, Ne, Ar, Kr, Xe) isotopic ratios and their volume fractions from the Antrim Shale gases to assess compositional variability and vertical fluid migration, in addition to distinguishing between the presence of thermogenic versus biogenic methane. R/Ra values of Antrim Shale gases (where R and Ra are the measured and atmospheric 3He/4He ratios, respectively) vary from 0.01 to 0.34 suggesting dominant crustal 4He in addition to minor mantle and atmospheric He. Elevated 20Ne/22Ne ratios (up to 10.4) point to mantle Ne. Similarly crustal 21Ne*, 40Ar* and 136Xe* are also suggested. High variability of noblegas signatures in the Antrim Shale are observed, which are mainly due to variable noblegas input from deep brines and, to a smaller extent, variable in-situ production in the Antrim Shale. Estimated 4He ages considering external 4He flux for Antrim water match well with timings of three major glaciation periods (Wisconsin, Illinoian and Kansan glaciations) in the Michigan Basin, suggesting that all our Antrim samples were more or less influenced by glaciation recharge. Consistency in measured and predicted 40Ar/36Ar assuming Ar release temperatures ≥ 250°C supports a thermogenic origin for the majority of the methane in our Antrim Shale gas samples. Thermogenic methane is likely to originate at greater depth, either from deeper portions of the Antrim Shale in the central Michigan Basin or from deeper formations underlying the Antrim Shale, as the thermal maturity of the Antrim Shale in our study area is low.

We report mineralogical and noblegas evidence for an ET impact associated with the Younger Dryas (YD) event and the mass extinction of various megafauna throughout the Americas approximately 12,900 years ago. We examined numerous well established, 14C dated Clovis sites across the US including detailed sediment profile analyses at Daisy Cave, CA (DC), Murray Springs, AZ (MS), Topper, SC, and Blackwater Draw, NM (BWD). He, Ne, and Ar analysis of magnetic separates, bulk sediments, HF-acid treated residue, and fullerenes coupled with a detailed mineralogical and compositional analysis of magnetic separates by SEM suggest a marked increase in the accretion of extraterrestrial debris in sediments at the YD boundary layer. A preliminary characterization of the magnetic separates consistently observed across numerous sites indicates an extremely high abundance of relatively unoxidized, trace metal rich metallic grains with extremely unusual compositions (e.g. Pt (5-98%), Sn (25-28%) , Ni (1-11%), and Cu (12-90%). These compositions are not easily explained by ordinary terrestrial processes. A few examples include the YD layer at DC which contains numerous metallic grains including Fe-Ni, Cu-Ni, Fe-Sn-Ni, and Pt grains. Metallic iron grains are observed at BWD and Topper, while the Topper site also contains iron spherules, Fe-Ni metallic grains, and Fe-Ni oxides. At this point there is no evidence for a significant concentration of iron spherules, Fe-Ni oxides nor unusual metallic grains away from the proposed impact layer. The noblegas composition and isotopic ratios of fullerenes located at the YD layers contain trapped He with ET isotopic signatures (0.3-3.5 ncc/g 3He and 3He/4He 30- 220 Ra) while Argon ratios (40Ar/36Ar= 230-255) reflect a mixture of planetary and air components. Bulk sediments were treated with HF acid to remove silicates, leaving a carbonaceous residue. Acid treated residues from two boundary layers contained up to 5 ncc/g 3He and 3He/4He from 15

We report mineralogical and noblegas evidence for an ET impact associated with the Younger Dryas (YD) event and the mass extinction of various megafauna throughout the Americas approximately 12,900 years ago. We examined numerous well established, 14C dated Clovis sites across the US including detailed sediment profile analyses at Daisy Cave, CA (DC), Murray Springs, AZ (MS), Topper, SC, and Blackwater Draw, NM (BWD). He, Ne, and Ar analysis of magnetic separates, bulk sediments, HF-acid treated residue, and fullerenes coupled with a detailed mineralogical and compositional analysis of magnetic separates by SEM suggest a marked increase in the accretion of extraterrestrial debris in sediments at the YD boundary layer. A preliminary characterization of the magnetic separates consistently observed across numerous sites indicates an extremely high abundance of relatively unoxidized, trace metal rich metallic grains with extremely unusual compositions (e.g. Pt (5-98%), Sn (25-28%) , Ni (1-11%), and Cu (12-90%). These compositions are not easily explained by ordinary terrestrial processes. A few examples include the YD layer at DC which contains numerous metallic grains including Fe-Ni, Cu-Ni, Fe-Sn-Ni, and Pt grains. Metallic iron grains are observed at BWD and Topper, while the Topper site also contains iron spherules, Fe-Ni metallic grains, and Fe-Ni oxides. At this point there is no evidence for a significant concentration of iron spherules, Fe-Ni oxides nor unusual metallic grains away from the proposed impact layer. The noblegas composition and isotopic ratios of fullerenes located at the YD layers contain trapped He with ET isotopic signatures (0.3-3.5 ncc/g 3He and 3He/4He 30- 220 Ra) while Argon ratios (40Ar/^{36}Ar= 230-255) reflect a mixture of planetary and air components. Bulk sediments were treated with HF acid to remove silicates, leaving a carbonaceous residue. Acid treated residues from two boundary layers contained up to 5 ncc/g 3He and 3He/4He from

System monitors welding gas to ensure characteristics within predetermined values. Responds to changes that might go unnoticed by human operator and acts quickly to prevent weld defects. Electronic pressure controller employs various amounts of gain, equalization, and compensation to respond to changes in gas-supply pressure. Works in conjuction with pressure/oxygen/moisture monitor.

The parent sulfonyl azide CH3SO2N3 has been characterized in a neat form by IR (gas, matrix-isolation) and Raman (solid) spectroscopy, and its structure has been established by X-ray crystallography. In both gas phase and solid state, the azide exhibits single conformation with the azido ligand being synperiplanar to one of the two S═O groups. In the crystal molecules of CH3SO2N3 are interconnected through three-dimensional O···H-C-H···O hydrogen bonds. Upon an ArF laser (193 nm) photolysis, the azide in solid noblegas matrices splits off N2 and yields the sulfonyl nitrene CH3SO2N in the triplet ground state. Subsequent photolysis with UV light (266 nm) causes the transformation from the nitrene to the pseudo-Curtius rearrangement product CH3NSO2. The identification of the photolysis intermediates by matrix-isolation IR spectroscopy is supported by quantum chemical calculations with DFT methods. PMID:27383463

Horizontal drilling and hydraulic fracturing have enhanced energy production but raised concerns about drinking-water contamination and other environmental impacts. Identifying the sources and mechanisms of contamination can help improve the environmental and economic sustainability of shale-gas extraction. We analyzed 113 and 20 samples from drinking-water wells overlying the Marcellus and Barnett Shales, respectively, examining hydrocarbon abundance and isotopic compositions (e.g., C2H6/CH4, δ(13)C-CH4) and providing, to our knowledge, the first comprehensive analyses of noble gases and their isotopes (e.g., (4)He, (20)Ne, (36)Ar) in groundwater near shale-gas wells. We addressed two questions. (i) Are elevated levels of hydrocarbon gases in drinking-water aquifers near gas wells natural or anthropogenic? (ii) If fugitive gas contamination exists, what mechanisms cause it? Against a backdrop of naturally occurring salt- and gas-rich groundwater, we identified eight discrete clusters of fugitive gas contamination, seven in Pennsylvania and one in Texas that showed increased contamination through time. Where fugitive gas contamination occurred, the relative proportions of thermogenic hydrocarbon gas (e.g., CH4, (4)He) were significantly higher (P < 0.01) and the proportions of atmospheric gases (air-saturated water; e.g., N2, (36)Ar) were significantly lower (P < 0.01) relative to background groundwater. Noblegas isotope and hydrocarbon data link four contamination clusters to gas leakage from intermediate-depth strata through failures of annulus cement, three to target production gases that seem to implicate faulty production casings, and one to an underground gas well failure. Noblegas data appear to rule out gas contamination by upward migration from depth through overlying geological strata triggered by horizontal drilling or hydraulic fracturing. PMID:25225410

Horizontal drilling and hydraulic fracturing have enhanced energy production but raised concerns about drinking-water contamination and other environmental impacts. Identifying the sources and mechanisms of contamination can help improve the environmental and economic sustainability of shale-gas extraction. We analyzed 113 and 20 samples from drinking-water wells overlying the Marcellus and Barnett Shales, respectively, examining hydrocarbon abundance and isotopic compositions (e.g., C2H6/CH4, δ13C-CH4) and providing, to our knowledge, the first comprehensive analyses of noble gases and their isotopes (e.g., 4He, 20Ne, 36Ar) in groundwater near shale-gas wells. We addressed two questions. (i) Are elevated levels of hydrocarbon gases in drinking-water aquifers near gas wells natural or anthropogenic? (ii) If fugitive gas contamination exists, what mechanisms cause it? Against a backdrop of naturally occurring salt- and gas-rich groundwater, we identified eight discrete clusters of fugitive gas contamination, seven in Pennsylvania and one in Texas that showed increased contamination through time. Where fugitive gas contamination occurred, the relative proportions of thermogenic hydrocarbon gas (e.g., CH4, 4He) were significantly higher (P < 0.01) and the proportions of atmospheric gases (air-saturated water; e.g., N2, 36Ar) were significantly lower (P < 0.01) relative to background groundwater. Noblegas isotope and hydrocarbon data link four contamination clusters to gas leakage from intermediate-depth strata through failures of annulus cement, three to target production gases that seem to implicate faulty production casings, and one to an underground gas well failure. Noblegas data appear to rule out gas contamination by upward migration from depth through overlying geological strata triggered by horizontal drilling or hydraulic fracturing. PMID:25225410

We have investigated seven micrometeorites (MMs) from Antarctic snow collected in 2003 and 2010 by means of electron microscopy, X-ray diffraction, micro-Raman spectroscopy, transmission electron microscopy (TEM) observation, and noble-gas isotope analysis. Isotopic ratios of He and Ne indicate that the noble gases in these MMs are mostly of solar wind (SW). Based on the release patterns of SW 4He, which should reflect the degree of heating during atmospheric entry, the seven MMs were classified into three types including two least heated, three moderately heated, and two severely heated MMs. The heating degrees are well correlated to their mineralogical features determined by TEM observation. One of the least heated MMs is composed of phyllosilicates, whereas the other consists of anhydrous minerals within which solar flare tracks were observed. The two severely heated MMs show clear evidence of atmospheric heating such as partial melt of the uppermost surface layer in one and abundant patches of dendritic magnetite and Si-rich glass within an olivine grain in the other. It is noteworthy that a moderately heated MM composed of a single crystal of olivine has a 3He/4He ratio of 8.44 × 10-4, which is higher than the SW value of 4.64 × 10-4, but does not show a cosmogenic 21Ne signature such as 20Ne/21Ne/22Ne = 12.83/0.0284/1. The isotopic compositions of He and Ne in this sample cannot be explained by mixing of a galactic cosmic ray (GCR)-produced component and SW gases. The high 3He/4He ratio without cosmogenic 21Ne signature likely indicates the presence of a 3He-enriched component derived from solar energetic particles.

Dissolved noble gases (NGs) in groundwater provide a well-established tool for paleo temperature reconstruction. However, reliable noblegas temperature (NGT) determination needs appropriate assumptions or rather an exact knowledge of soil air composition. Deviations of soil air NG partial pressures from atmospheric values have already been found in mid latitudes during summer time as a consequence of subsurface oxygen depletion. This effect depends on ambient temperature and humidity and is thus expected to be especially strong in humid tropical soils, which was not investigated so far. We therefore studied NGs in soil air and shallow groundwater near Santarém (Pará, Brazil) at the end of the rainy and dry seasons, respectively. Soil air data confirms a correlation between NG partial pressures, the sum value of O2+CO2 and soil moisture contents. During the rainy season, we find significant NG enhancements in soil air by up to 7% with respect to the atmosphere. This is twice as much as observed during the dry season. Groundwater samples show neon excess values between 15% and 120%. Nearly all wells show no seasonal variations of excess air, even though the local river level seasonally fluctuates by about 8 m. Assuming atmospheric NG contents in soil air, fitted NGTs underestimate the measured groundwater temperature by about 1-2° C. However, including enhanced soil air NG contents as observed during the rainy season, resulting NGTs are in good agreement with local groundwater temperatures. Our presented data allows for a better understanding of subsurface NG variations. This is essential with regard to NG tracer applications in humid tropical areas, for which reliable paleoclimate data is of major importance for modern climate research.

Early results from an ongoing search for isotopically distinctive noble gases as evidence for presolar oxide grains are presented. With some qualifications, we do not see such evidence in spinel rich acid residue fractions from the Allende meteorite. We remain hopeful that less abundant mineral separates may yet be fruitful. Presolar grains, micro-diamonds, silicon carbide, and graphite, were found in primitive meteorites. While the abundances of these three refractory C rich grains are low, a few hundred ppm, a few ppm, & less than 1 ppm, respectively in primitive meteorites, they are tagged with high concentrations of isotopically anomalous noblegas components, Xe-HL, KR & Xe-s and Ne-E(H), and Ne-E(L). These tags have served as tracers and allowed the development of techniques for their purification and eventual identification. One might expect similar amounts of refractory presolar oxides to have survived, but so far only three cases exist for their identification. The first two cases are individual corundum oxide grains. Huss et al. found one such grain from an Orgueil residue with an Al-26/Al-27 ratio of 8.9 x 10(exp -5), about 18 times higher than the canonical initial solar system value. The second corundum grain, from Murchison, was found by Nittler et al. to have unusual oxygen in addition to a similar Al-26/Al-27 ratio of 8.7 x 10(exp -4). The oxygen was depleted in O-18 by 22 percent and enriched in O-17 by a factor of 2. The third case is a measurement by Zinner et al. on an aggregate of fine grained spinels from a Murray residue with an O-17 enrichment and a possible O-18 depletion similar to the second grain, but much subdued. This is consistent with a few such presolar grains diluted by a much larger population of isotopically normal corundum grains and an even larger number of normal spinel grains.

This report addresses the standard operating procedures used by the U.S. Geological Survey’s NobleGas Laboratory in Denver, Colorado, U.S.A., for the measurement of dissolved gases (methane, nitrogen, oxygen, and carbon dioxide) and noblegas isotopes (helium-3, helium-4, neon-20, neon-21, neon-22, argon-36, argon-38, argon-40, kryton-84, krypton-86, xenon-103, and xenon-132) dissolved in water. A synopsis of the instrumentation used, procedures followed, calibration practices, standards used, and a quality assurance and quality control program is presented. The report outlines the day-to-day operation of the Residual Gas Analyzer Model 200, Mass Analyzer Products Model 215–50, and ultralow vacuum extraction line along with the sample handling procedures, noblegas extraction and purification, instrument measurement procedures, instrumental data acquisition, and calculations for the conversion of raw data from the mass spectrometer into noblegas concentrations per unit mass of water analyzed. Techniques for the preparation of artificial dissolved gas standards are detailed and coupled to a quality assurance and quality control program to present the accuracy of the procedures used in the laboratory.

The structural stability of pure SnO2 nanoparticles and highly sensitive SnO2-SiO2 nanocomposites (0–15 SiO2 wt%) has been investigated for conditions relevant to their utilization as chemoresistive gas sensors. Thermal stabilization by SiO2 co-synthesis has been investigated at up to 600 °C determining regimes of crystal size stability as a function of SiO2-content. For operation up to 400 °C, thermally stable crystal sizes of ca. 24 and 11 nm were identified for SnO2 nanoparticles and 1.4 wt% SnO2-SiO2 nanocomposites, respectively. The effect of crystal growth during operation (TO = 320 °C) on the sensor response to ethanol has been reported, revealing possible long-term destabilization mechanisms. In particular, crystal growth and sintering-neck formation were discussed with respect to their potential to change the sensor response and calibration. Furthermore, the effect of SiO2 cosynthesis on the cross-sensitivity to humidity of these noble metal-free SnO2-based gas sensors was assessed. PMID:25585712

The latest generation of multi-collector noblegas mass spectrometers has decisively improved the precision in isotopic ratio analysis [1, 2] and helped the scientific community to address new questions [3]. Measuring numerous isotopes simultaneously has two significant advantages: firstly, any fluctuations in signal intensity have no effect on the isotope ratio and secondly, the analysis time is reduced. This particular point becomes very important in static vacuum mass spectrometry where during the analysis, the signal intensity decays and at the same time the background increases. However, when multi-collector analysis is utilized, it is necessary to pay special attention to the cross calibration of the detectors. This is a key point in order to have accurate and reproducible isotopic ratios. In isotope ratio mass spectrometry, with regard to the type of detector (i.e. Faraday or Secondary Electron Multiplier, SEM), analytical technique (TIMS, MC-ICP-MS or IRMS) and isotope system of interest, several techniques are currently applied to cross-calibrate the detectors. Specifically, the gain of the Faraday cups is generally stable and only the associated amplifier must be calibrated. For example, on the Thermo Scientific instrument control systems, the 1011 and 1012 ohm amplifiers can easily be calibrated through a fully software controlled procedure by inputting a constant electric signal to each amplifier sequentially [4]. On the other hand, the yield of the SEMs can drift up to 0.2% / hour and other techniques such as peak hopping, standard-sample bracketing and multi-dynamic measurement must be used. Peak hopping allows the detectors to be calibrated by measuring an ion beam of constant intensity across the detectors whereas standard-sample bracketing corrects the drift of the detectors through the analysis of a reference standard of a known isotopic ratio. If at least one isotopic pair of the sample is known, multi-dynamic measurement can be used; in this

Nitrogen and noblegas (Ne-Ar) abundances and isotope ratios, determined by step-wise CO2 laser-extraction, static-mass spectrometry analysis, are reported for bulk fragments and mineral separates of ten lunar mare basalts (10020, 10057, 12008, 14053, 15555, 70255, 71557, 71576, 74255, 74275), one highland breccia (14321), and one ferroan anorthosite (15414). The mare basalt sub-samples 10057,183 and 71576,12 contain a large amount of solar noble gases, whereas neon and argon in all other samples are purely cosmogenic, as shown by their 21Ne/22Ne ratios of ≈0.85 and 36Ar/38Ar ratios of ≈0.65. The solar-gas-free basalts contain a two-component mixture of cosmogenic 15N and indigenous nitrogen (<0.5 ppm). Mare basalt 74255 and the olivine fraction of 15555,876 record the smallest proportion of 15Ncosm; therefore, their δ15 N values of -0.2 to + 26.7 ‰ (observed at the low-temperature steps) are thought to well represent the isotopic composition of indigenous lunar nitrogen. However, δ15 N values ≤ - 30 ‰ are found in several basalts, overlapping with the isotopic signature of Earth's primordial mantle or an enstatite chondrite-like impactor. While the lowest δ15 N values allow for nitrogen trapped in the Moon's interior to be inherited from the proto-Earth and/or the impactor, the more 15N-enriched compositions require that carbonaceous chondrites provided nitrogen to the lunar magma ocean prior to the solidification of the crust. Since nitrogen can efficiently be incorporated into mafic minerals (olivine, pyroxene) under oxygen fugacities close to or below the iron-wustite buffer (Li et al., 2013), the mare basalt source region is likely characterized by a high nitrogen storage capacity. In contrast, anorthosite 15414 shows no traces of indigenous nitrogen, suggesting that nitrogen was not efficiently incorporated into the lunar crust during magma ocean differentiation.

Secure storage of anthropogenic carbon dioxide (CO2) in geological reservoirs requires predicting gas-water-rock interactions over millennial timescales. Noble gases and carbon isotope measurements can be used to shed light on the nature of competing dissolution-precipitation processes over different timescales, from the fast dissolution of gaseous CO2 in groundwater to more sluggish reactions involving dissolution and precipitation of newly formed minerals in the reservoir. Here we study a compilation of gas analyses including noble gases and δ13C of CO2 from nine different natural CO2 reservoirs. Amongst these reservoirs, the Bravo Dome CO2 field (New Mexico, USA) shows distinct geochemical trends which are explained by degassing of noble gases from groundwater altering the composition of the gas phase. This groundwater degassing is synchronous with the dissolution of CO2 in groundwater. Progressive creation of alkalinity via CO2-promoted mineral dissolution is required to explain the observed positive correlation between CO2/3He and δ13C of the gas phase, a unique feature of Bravo Dome. The differences between Bravo Dome and other natural CO2 reservoirs are likely explained by the more recent filling of Bravo Dome, reflecting CO2-water-rock interactions over thousands of years rather than over millions of years in older reservoirs.

Silurian and Devonian natural gas reservoirs present within New York state represent an example of unconventional gas accumulations within the northern Appalachian Basin. These unconventional energy resources, previously thought to be noneconomically viable, have come into play following advances in drilling (i.e., horizontal drilling) and extraction (i.e., hydraulic fracturing) capabilities. Therefore, efforts to understand these and other domestic and global natural gas reserves have recently increased. The suspicion of fugitive mass migration issues within current Appalachian production fields has catalyzed the need to develop a greater understanding of the genetic grouping (source) and migrational history of natural gases in this area. We introduce new noblegas data in the context of published hydrocarbon carbon (C1,C2+) (13C) data to explore the genesis of thermogenic gases in the Appalachian Basin. This study includes natural gases from two distinct genetic groups: group 1, Upper Devonian (Marcellus shale and Canadaway Group) gases generated in situ, characterized by early mature (13C[C1 C2][13C113C2]: –9), isotopically light methane, with low (4He) (average, 1 103 cc/cc) elevated 4He/40Ar and 21Ne/40Ar (where the asterisk denotes excess radiogenic or nucleogenic production beyond the atmospheric ratio), and a variable, atmospherically (air-saturated–water) derived noblegas component; and group 2, a migratory natural gas that emanated from Lower Ordovician source rocks (i.e., most likely, Middle Ordovician Trenton or Black River group) that is currently hosted primarily in Lower Silurian sands (i.e., Medina or Clinton group) characterized by isotopically heavy, mature methane (13C[C1 – C2] [13C113C2]: 3), with high (4He) (average, 1.85 103 cc/cc) 4He/40Ar and 21Ne/40Ar near crustal production levels and elevated crustal noblegas content (enriched 4He,21Ne, 40Ar). Because the release of each crustal noblegas (i.e., He, Ne, Ar

The database (Version 1.0) is a MS-Excel file that contains close to 5,000 entries of published information on noblegas concentrations and isotopic ratios from volcanic systems in Mid-Ocean ridges, ocean islands, seamounts, and oceanic and continental arcs (location map). Where they were available we also included the isotopic ratios of strontium, neodymium, and carbon. The database is sub-divided both into material sampled (e.g., volcanic glass, different minerals, fumarole, spring), and into different tectonic settings (MOR, ocean islands, volcanic arcs). Included is also a reference list in MS-Word and pdf from which the data was derived. The database extends previous compilations by Ozima (1994), Farley and Neroda (1998), and Graham (2002). The extended database allows scientists to test competing hypotheses, and it provides a framework for analysis of noblegas data during periods of volcanic unrest.

Recent noblegas studies suggests the Earth's atmosphere outgassed from the Earth's upper mantle synchronous with sea floor spreading, ocean ridge hydrothermal activity and the formation of continents by partial melting in subduction zones. The evidence for formation of the atmosphere by outgassing of the mantle is the presence of radionuclides H3.-4, Ar-040 and 136 Xe-136 in the atmosphere that were produced from K-40, U and Th in the mantle. How these radionuclides were formed is reviewed.

Our knowledge of the noblegas abundances and isotopic compositions in the Martian crust and atmosphere come from two sources, measurements of meteorites from Mars and in situ measurements by spacecraft. Measurements by the Viking landers had large uncertainties, but were precise enough to tie the meteorites to Mars. Hence most of the questions we have are currently defined by meteorite measurements. Curiosity's SAM has confirmed that the Ar isotopic composition of the atmosphere is highly fractionated, presumably representing atmospheric loss that can now be modeled with more confidence. What turns out to be a more difficult trait to explain is the fact that the ratio of Kr/Xe in nakhlites, chassignites and ALH84001 is distinct from the atmospheric ratio, as defined by measurements from shergottites. This discrepancy has been suggested to be a result of atmosphere/groundwater/rock interaction, polar clathrate formation, or perhaps local temperature conditions. More detailed atmospheric measurements, along with targeted simulation experiments, will be needed to make full use of this anomaly.

New, high-sensitivity and high-resolution spectroscopic and imaging methods may be developed by exploiting nuclear magneto-optic effects. A first-principles electronic structure formulation of nuclear electric quadrupole moment-induced Cotton-Mouton effect (NQCME) is presented for closed-shell atoms. In NQCME, aligned quadrupole moments alter the index of refraction of the medium along with and perpendicular to the direction of nuclear alignment. The roles of basis-set convergence, electron correlation, and relativistic effects are investigated for three quadrupolar noblegas isotopes: {sup 21}Ne, {sup 83}Kr, and {sup 131}Xe. The magnitude of the resulting ellipticities is predicted to be 10{sup −4}–10{sup −6} rad/(M cm) for fully spin-polarized nuclei. These should be detectable in the Voigt setup. Particularly interesting is the case of {sup 131}Xe, in which a high degree of spin polarization can be achieved via spin-exchange optical hyperpolarization.

Valence-bound (VB) and diffuse-bound (DB) anions of noble-gas (Ar, Kr, and Xe) complexes with uracil have been studied with ab initio methods. MP2 optimizations revealed minima corresponding to anions of both kinds in each case. Coupled-cluster singles and doubles with perturbative triples, CCSD(T), and electron propagator single-point calculations were performed in order to assess vertical and adiabatic electron detachment energies of these complexes. Ab initio electron propagator calculations employed the outer valence Green's function and partial third-order approximations, and the algebraic diagrammatic construction in third order. Basis set effects have been systematically examined. DB anions of all three complexes were adiabatically bound, with calculated adiabatic electron attachment energies below 0.06 eV. Corresponding vertical electron detachment energies were below 0.1 eV. As to VB anions, only the Xe complex had a positive adiabatic electron detachment energy, of 0.01 eV, with a corresponding vertical electron detachment energy of 0.6 eV. These computational findings are consistent with the interpretation of results previously obtained experimentally by Hendricks et al.

In situ high-energy X-ray diffraction coupled to atomic pair distribution function analysis is used to obtain fundamental insight into the effect of the reactive gas environment on the atomic-scale structure of metallic particles less than 10 nm in size. To substantiate our recent discovery we investigate a wide range of noble-transition metal nanoparticles and confirm that they expand and contract radially when treated in oxidizing (O2) and reducing (H2) atmospheres, respectively. The results are confirmed by supplementary XAFS experiments. Using computer simulations guided by the experimental diffraction data we quantify the effect in terms of both relative lattice strain and absolute atomic displacements. In particular, we show that the effect leads to a small percent of extra surface strain corresponding to several tenths of Ångström displacements of the atoms at the outmost layer of the particles. The effect then gradually decays to zero within 4 atomic layers inside the particles. We also show that, reminiscent of a breathing type structural transformation, the effect is reproducible and reversible. We argue that because of its significance and widespread occurrence the effect should be taken into account in nanoparticle research. PMID:23828235

The discovery of ArH+ in the interstellar medium has shown that noblegas chemistry may be of more chemical significance than previously believed. The present work extends the known chemistry of small noblegas molecules to NeOH+ and ArOH+. Besides their respective neonium and argonium diatomic cation cousins, these hydroxyl cation molecules are the most stable small noblegas molecules analyzed of late. ArOH+ is once again more stable than the neon cation, but both are well-behaved enough for a complete quartic force field analysis of their rovibrational properties. The Ar-O bond in ArOH+ , for instance, is roughly three-quarters of the strength of the Ar-H bond in ArH+ highlighting the rigidity of this system. The rotational constants, geometries, and vibrational frequencies for both molecules and their various isotopologues are computed from ab initio quantum chemical theory at high-level, and it is shown that these cations may form in regions where peroxy or weakly-bound alcohols may be present. The resulting data should be of significant assistance for the laboratory or observational analysis of these potential interstellar molecules.

Noblegas isotopes including 3He 4He, 40Ar 36Ar and Xe isotope ratios were determined for coexisting glass and olivine crystals in tholeiitic and alkalic basalts and dunite xenoliths from Loihi Seamount. Glass and coexisting olivine crystals have similar 3He 4He ratios (2.8-3.4) ?? 10-5, 20 to 24 times the atmospheric ratio (RA), but different 40Ar 36Ar ratios (400-1000). Based on the results of noblegas isotope ratios and microscopic observation, some olivine crystals are xenocrysts. We conclude that He is equilibrated between glass and olivine xenocrysts, but Ar is not. The apparent high 3He 4He ratio (3 ?? 10-5; = 21 RA) coupled with a relatively high 40Ar 36Ar ratio (4200) for dunite xenoliths (KK 17-5) may be explained by equilibration of He between MORB-type cumulates and the host magma. Except for the dunite xenoliths, noblegas data for these Loihi samples are compatible with a model in which samples from hot spot areas may be explained by mixing between P (plume)-type and M (MORB)-type components with the addition of A (atmosphere)-type component. Excess 129Xe has not been observed due to apparent large mass fractionation among Xe isotopes. ?? 1983.

Using optical-emission spectroscopy, the interaction between metastable-excited noblegas and fluorocarbon species is investigated for poly-chloro-tri-fluoro-ethylene (PCTFE) sputtering under a mixture of noblegas and CF3Cl gas flow conditions. Among a variety of noble gases, He and Ne in an excited state were quenched through energy transfer which induced the ionization and self-decomposition of the halogenated carbon species. Such an inactivation was not observed in the Ar, Kr, and Xe cases, in accordance with the ionization energy in CF3Cl derived from photoelectron spectroscopy. Instability in a radio-frequency (rf) plasma was observed in the pure Xe case. However, the plasma was stabilized in the case of a mixture with CF3Cl. The CF2 band which is characteristic of PCTFE sputtering was not detected in the Xe case. In addition, it was confirmed that the oxygen introduced into the rf plasma was more likely to react with CF2(3B1) than with CF2(1B1) or CF3(1B1).

Neon isotopes provide a unique opportunity to distinguish between volatiles introduced into the mantle during the accretion of the Earth by equilibration between a magma ocean with a massive early atmosphere, or as a component trapped within accreting material. A massive early atmosphere would have a Solar Ne isotopic composition (20Ne/22Ne=13.8) while accreting material that has been irradiated by solar wind preserves a distinct composite mix, often called Ne-B (20Ne/22Ne=12.5). To date the highest reliable Ne isotopic values measured in mid ocean ridge basalt (MORB) samples reach a maximum at values of about 12.5. It is not possible to rule out using the MORB sample suite the possibility that ubiquitous air contamination (20Ne/22Ne=9.8) found in this sample type suppresses the maximum Ne value measured. We present noblegas data from 14 CO2 well gases collected from Harding County, New Mexico. With 3He/4He ranging from 0.76 to 3.7Ra (Ra= atmospheric ratio) and correlated 40Ar/36Ar ratios that vary from 4660 to 22600, these samples represent a mixture of crustal and mantle-derived noble gases with only a small groundwater-derived air component. The precision with which we can analyse these gases combined with a systematic and well-mixed crust/groundwater component allows us to resolve crustal, mantle and air components for He, Ne and Ar. The resolved elemental ratios of the mantle He/Ne and He/Ar components are similar to those resolved in volatile rich mid ocean ridge popping rocks. A near constant crust+air end-member component defines a Ne isotope mixing line that intersects with the MORB-air mixing line at 20Ne/22Ne=12.20 plus or minus 0.05. The small difference between the 20Ne/22Ne upper-limit resolved in the well gases compared to that observed in MORB can be accounted for by slightly different mantle He/Ne ratios. While this result provides the first unambiguous evidence for the upper mantle 20Ne/22Ne limit, sources other than Ne-B must also be considered

Gas House Autonomous System Monitoring (GHASM) will employ Integrated System Health Monitoring (ISHM) of cryogenic fluids in the High Pressure Gas Facility at Stennis Space Center. The preliminary focus of development incorporates the passive monitoring and eventual commanding of the Nitrogen System. ISHM offers generic system awareness, adept at using concepts rather than specific error cases. As an enabler for autonomy, ISHM provides capabilities inclusive of anomaly detection, diagnosis, and abnormality prediction. Advancing ISHM and Autonomous Operation functional capabilities enhances quality of data, optimizes safety, improves cost effectiveness, and has direct benefits to a wide spectrum of aerospace applications.

The deep Earth is the key to understanding the primordial evolution of the Earth's atmosphere. However the atmosphere was not derived by degassing of the Earth, as widely held. Isotopic characterization of mantle noble gases and modeling based on this information [1] suggests the atmosphere experienced a 3-stage early history. This follows from 5 basic observations: (i) Ne in the mantle is solar-like, with light (high) 20Ne/22Ne relative to the atmosphere [2]; (ii) mantle Xe has higher 128Xe/130Xe than the atmosphere [3], which carries an extreme heavy isotope enriched mass fractionation signature of >3%/amu (iii) most of the radiogenic Xe from l29I and 244Pu decay in the Earth is not present either in the mantle or in the atmosphere; (iv) the inferred abundances of noble gases in the deep Earth "plume source" are insufficient to generate the present atmospheric abundances, even for whole mantle degassing; and (v) mantle noble gases indicate a 2 component structure, with solar light gases (He and Ne) and planetary heavy gases [4]. The present day noblegas budgets (and likely also N2) must derive from late accretion of a volatile-rich "veneer." This is stage III. Stage II is a naked (no atmosphere) epoch indicated by evidence for Hadean degassing of 244Pu (T1/2 = 80 Ma) fission Xe from the whole mantle, which was not retained in the present atmosphere. The naked stage must have lasted for more than ~200 Ma, and was supported by the early intense solar EUV luminosity. Stage I, a massive solar-composition protoatmosphere, occurred during the Earth's early accretion phase. Its existence is indicated by the presence of the solar gas component in the Earth. This is not attributable to subduction of solar wind rich cosmic dust, or solar wind irradiation of coagulating objects. It is best explained by accretion of a solar composition atmosphere from the nebula. This provided a thermal blanket supporting a magma ocean in which solar gases dissolved. Under these conditions

Numerical models successfully simulate LGM glacier extents in the Sierra Nevada, California, over a large range of precipitation and temperature combinations (Kessler et al. 2006, J. Geophys. Res., 111, F02002, doi:10.1029/2005JF000365). We use cosmogenic noblegas paleothermometry on samples from summit flats in the Sierra Nevada to estimate temperatures during the last glacial period in this region and further constrain the climatological predictions of these models. Cosmogenic noblegas paleothermometry utilizes the open-system behavior of cosmogenic noble gases at surface temperatures in common minerals like quartz to quantify the thermal histories of rocks during exposure to cosmic ray particles at the Earth's surface. We sampled boulders and bedrock tors atop summit flats inferred to be exposed throughout the last glacial period and measured cosmogenic 3He and 21Ne concentrations in quartz from these samples. We use cosmogenic 21Ne, which is quantitatively retained at Earth surface temperatures in quartz, to constrain exposure durations and erosion rates, and cosmogenic 3He, which exhibits open-system behavior in quartz, to quantify time-integrated temperatures during surface exposure. Data from samples collected at the summit of Mt. Langley in the southern Sierra Nevada indicate that 30-45% of the cosmogenic 3He produced in quartz has been retained at surface exposure temperatures; the rest has been diffusively lost. Preliminary models using these data and published diffusion kinetics indicate that the difference between modern and LGM summit temperatures may be significantly greater than the 5.6°C difference predicted by Kessler et al. (2006). We would expect significantly less 3He to be retained if average temperatures were 5.6°C lower at the LGM. Additional cosmogenic noblegas measurements on samples from this site and other sites in the Sierra Nevada and White Mountains as well as sample-specific diffusion kinetics will enable us to quantify this

Paleotempertures retrieved from the groundwater archives in the largest watershed (≈800 km2) in the Olympic Mountains suggest asynchronous Olympic Peninsula climate responses during the Everson interstade period after the last continental glacial maximum. Dissolved noble gases fr...

Space technology is contributing to air pollution control primarily through improved detectors and analysis methods. Miniaturized mass spectrometer is under development to monitor vinyl chloride and other hydrocarbon contaminants in an airborne laboratory. Miniaturized mass spectrometer can be used to protect personnel in naval and medical operations as well as aboard aircraft.

The development of a technically sound approach to detecting the subsurface release of noblegas radionuclides is a critical component of the on-site inspection (OSI) protocol under the Comprehensive Nuclear Test Ban Treaty. In this context, we are investigating a variety of technical challenges that have a significant bearing on policy development and technical guidance regarding the detection of noble gases and the creation of a technically justifiable OSI concept of operation. The work focuses on optimizing the ability to capture radioactive noble gases subject to the constraints of possible OSI scenarios. This focus results from recognizing the difficulty of detecting gas releases in geologic environments—a lesson we learned previously from the non-proliferation experiment (NPE). Most of our evaluations of a sampling or transport issue necessarily involve computer simulations. This is partly due to the lack of OSI-relevant field data, such as that provided by the NPE, and partly a result of the ability of computer-based models to test a range of geologic and atmospheric scenarios far beyond what could ever be studied by field experiments, making this approach very highly cost effective. We review some highlights of the transport and sampling issues we have investigated and complete the discussion of these issues with a description of a preliminary design for subsurface sampling that addresses some of the sampling challenges discussed here.

Ar, Kr, Xe, Cl, Br, I, and K abundances and isotopic compositions have been measured in microscopic fluid inclusions in minerals by noblegas mass spectrometry following neutron irradiation and laser extraction. The laser microprobe noblegas mass spectrometric (LMNGMS) technique was quantified by use of microstandards, including air-filled capillary tubes, synthetic basalt glass grains, standard hornblende grains, and synthetic fluid inclusions in quartz. Common natural concentrations of halogens (Cl, Br, and I) and noble gases (Ar and Kr) in trapped groundwaters and hydrothermal fluids can be analyzed simultaneously by LMNGMS in as little as 10-11 L of inclusion fluid, with accuracy and precision to within 5-10% for element and isotope ratios. Multicomponent element and isotope correlations indicate contaminants or persistent reservoirs of excess Xe and/or unfractionated air in some synthetic and natural fluid inclusion samples. LMNGMS analyses of natural fluid inclusions using the methods and calibrations reported here may be used to obtain unique information on sources of fluids, sources of fluid salinity, mixing, boiling (or unmixing), and water-rock interactions in ancient fluid flow systems. ?? 1992.

The 2516 m deep Outokumpu Deep Drill Hole is situated at the NW-SE trending boundary between the Archaean and Proterozoic domains of the eastern Fennoscandian Shield (Finland). In August 2011, eight fluid samples were collected with a Leutert positive displacement sampler (PDS) from 500 m to 2480 m depth in the open bore hole. The PDS allows sampling at in situ pressures, thus minimising fractionation from degassing during sampling. At the surface, the samples were transferred into an evacuated sampling line connected with a Cu-tube and a glass bulb for gas sampling, a pressure gauge, and a thermometer. Gas was liberated with a heated ultrasonic bath and then admitted to the sampling devices. Gas/water ratios were already determined in the field during gas extraction. Saline groundwaters rich in methane, nitrogen, hydrogen and helium and with water stable isotope composition distinctive from meteoric and sea water have been found to host isolated ecosystems within the Precambrian crystalline bedrock of Outokumpu (Kietäväinen et al., 2013). In order to characterise the geochemical and microbiological evolution of the deep subsurface of the area, noblegas residence times have been calculated based on radiogenic (4He, 40Ar), nucleogenic (21Ne) and fissiogenic (134Xe, 136Xe) noblegas nuclides. Geochemical and microbiological variations together with hydrogeological and geophysical data indicate negligible vertical fluid flow in the bedrock. Moreover, noblegas diffusion models show that diffusion is not likely to affect noblegas concentrations of groundwater at or below 500 m depth in Outokumpu. Therefore in situ accumulation was assumed as a basis for the age determination. In general, residence times between 10 and 50 Ma were indicated by 4He and21Ne, while somewhat younger ages were obtained by 40Ar, using average values for porosity, density and concentration of radioactive elements in the bedrock of Outokumpu. Kietäväinen R., Ahonen L., Kukkonen I

Interatomic potentials that are relevant for noblegas bombardment of Cu and Ni targets have been calculated in the energy region below 10 keV. Potentials are calculated for the diatomic species: NeCu, ArCu, KrCu, Cu2, ArNi, Ni2 and NiCu. The calculations primarily employ density functional theory (with the B3LYP exchange-correlation functional). Potential curves derived from Hartree-Fock theory calculations are also discussed. Scalar relativistic effects have been included via the second-order Douglas-Kroll-Hess (DKH2) method. On the basis of a variational argument, it can be shown that the predicted potential curves represent an upper limit to the true potential curves. The potentials provide a basis for assessing corrections required to the ZBL and Molière screened Coulombic potentials, which are typically found to be too repulsive below 1-2 keV. These corrections significantly improve the accuracy of the sputter yield predicted by molecular dynamics for Ni(1 0 0), whereas the sputter yield predicted for Cu(1 0 0) is negligibly affected. The validity of the pair potential approximation in the repulsive region of the potential is tested by direct calculation of the potentials arising from the interaction of either an Ar or Cu atom with a Cu3 cluster. The pairwise approximation represents the Ar-Cu3 potential energy function with an error <3 eV at all Ar-Cu3 separations. For Cu-Cu3, the pairwise approximation underestimates the potential by ca. 10 eV when the interstitial atom is located near the centre of the cluster.

Thirty-five deep ocean sediment samples from the Central Pacific sediment core LL-44 GPC-3 were examined for their noblegas composition and mineralogy. The samples spanned from 30 to 71 Ma in age, including the Cretaceous/Tertiary (K/T), Paleocene/Eocene (P/E), and Eocene/Oligocene (E/O) boundaries. From each bulk sediment sample, magnetic grains (5-200 μg/g; 1-20 μm diameter) were isolated and analyzed. Noblegas measurements determined the helium and neon isotopic compositions and the abundance of extra-terrestrial (ET) noble gases for the bulk and magnetic fractions. 3He/4He ratios of 3.1x10-4 and 20Ne/22Ne ratios of 9.96-12.62 are consistent with the SEP (solar energetic particle) signature seen in both zero-age magnetic grains (Z-MAG) from the central Pacific sediments and stratospheric interplanetary dust particles (IDPs). The isolated magnetic fraction typically consisted of less than 1% of the bulk sample while accounting for 3 to 10% of the bulk sediment 3He with a maximum of 40% at K/T boundary. The magnetic isolates revealed no significant differences of 3He/4He, 20Ne/22Ne, or (3He/20Ne)solar from the bulk GPC-3 sediments or Z-MAG grains. No temporal variation in He or Ne or anomalous gas signatures associated with the boundaries present within this time interval was observed. Scanning electron microscope analysis was utilized to determine the mineralogy of the magnetic isolates in an effort to distinguish between the continuous flux of interplanetary dust particles and the flux associated with major impact events. This information may also assist in determining the carrier phase of ET noble gases. Anomalously high Ni, Mg, Al, and Cr compositions combined with low or nonexistent abundances of titanium can distinguish extraterrestrial spinel grains from terrestrial spinel. The SEM analysis revealed stark contrasts in composition and morphology in the samples associated with the boundaries included in this study. A survey of ``background'' samples

The Noble Gases symposium, on which this report is based, provided comprehensive coverage of the noble gases. The coverage included, but was not limited to, the properties, biokinetics, bioeffects, production and release to the environment, detection techniques, standards, and ap...

Analyses of noblegas isotopes by multi-collector mass spectrometry substantially improve measurement precision and accuracy, with the potential to revolutionise applications to cosmo-geo-sciences. The Helix-MC noblegas mass spectrometer manufactured by Thermo-Fisher is a 350mm, 120 degree extended geometry, high resolution, multi-collector mass spectrometer for the simultaneous analysis of noblegas isotopes. The detector array includes a fixed axial (Ax) detector, 2 adjustable high mass (H1 and H2) detectors and 2 adjustable low mass (L1 and L2) detectors. Each detector is equipped with a Faraday/ion counting multiplier CFM (Combined Faraday and CDD Multiplier) detector. Mass resolution and mass resolving power on the H2, Ax and L2 detectors of the Helix-MC installed at the Australian National University (ANU) are approximately 1,800 and 8,000, respectively. The noblegas handling system on-line to the Helix-MC consists of: (1) a resistively-heated, double-vacuum, tantalum furnace system, (2) air actuated vacuum crusher, (3) Photon-Machines diode laser heating system, (4) Janis He cryogenic trap assembly, (5) gas purification system and (6) standard gas pipette tanks, which are totally automated and controlled by the Qtegra software platform developed by Thermo-Fisher. Eleven repeat measurements of atmospheric Ar using the H2 Faraday (1E11 ohm resistor) and L2 CDD collectors on the Helix-MC, yield a mean 40Ar/36Ar ratio of 322.09 +- 0.28 (0.089%) with a 4,700 fA 40Ar beam current. This result compares favourably with the precision achieved by the Argus VI at the University of Melbourne (318.12 +- 0.17; 0.052%; n = 10) with a similar beam size of 4,200 fA. The high mass resolution of the L2 collector permits complete separation of the 36Ar and interfering 3 x 12C (required mass resolution (MR) of 1,100) and partial separation of H35Cl (MR = 3,900). This capability enables evaluation of the significance of Ar isotopic interferences related to the correction of

With rising demands for cleaner domestic energy resources, horizontal drilling and hydraulic fracturing techniques in unconventional hydrocarbon exploration have been extensively developed. However, the observation that some water wells have showed elevated concentrations of dissolved methane and other light hydrocarbons has caused public concern regarding unconventional energy extraction. In this contribution, we present noblegas data of production shale gases from the Barnett and Strawn Formations, as well as nearby groundwater samples in south-central Texas. The Barnett Shale located in the Fort Worth Basin at an average depth of ~2300 m is one of the most prominent shale gas plays in the U.S. This DOE-sponsored study explores the potential of noble gases for fingerprinting shale gas and thus, for identifying the sources of gas in aquifers overlying the Barnett Shale, due either to natural hydrocarbon occurrences or potentially related to gas production from unconventional energy resources. A total of 35 groundwater samples were collected in Parker and Hood counties in areas where high amounts of methane (>10 mg/L) were detected in shallow groundwater. Two gas samples were also collected directly from groundwater wells where bubbling methane was present. Preliminary results show that He concentrations in water samples, in excess of up to three orders of magnitude higher than expected atmospheric values are directly correlated with methane concentrations. 3He/4He ratio values vary from 0.030 to 0.889 times the atmospheric ratio with the lowest, more pure radiogenic contributions being associated with highest methane levels. The presence of crustally-produced radiogenic 40Ar is also apparent in groundwater samples with 40Ar/36Ar ratios up to 316. A combined analysis of 40Ar/36Ar ratios from groundwater wells bubbling gas and that of shale gas suggests that the source of this methane is not the heavily exploited Barnett Shale, but rather, the Strawn Formation.

MP2, coupled-cluster, and multireference-CI calculations were performed to investigate the structure, stability, and properties of the noblegas anions FNgS- (Ng = He, Ar, Kr, Xe). Similar to the recently investigated FNgO- and FNgBN-, these species reside into deep wells on the singlet surface, protected by sizable barriers with respect to FS- + Ng and F- + Ng + S(3P). Their stability arises from the strong F--stabilization of the elusive NgS. The lightest FHeS- and FArS- are also first predicted examples of helium-sulfur and argon-sulfur molecular species.

The geochemical structure of the upper mantle in general and its noblegas isotopic structure in particular have been the subject of countless studies, as both provide important insights into mantle dynamic processes and are essential for the formulation of mantle geodynamic models. This contribution presents a noblegas study of basaltic glasses derived from the Mid-Atlantic-Ridge (MAR) between 4 and 12° S, an area well known for its high degree of lithophile isotope heterogeneity and exhibiting anomalous crustal thickness. The Sr, Nd, Pb and Hf isotopies along this segment of the MAR range from ultra-depleted (more than NMORB) to highly enriched, and different concepts have been proposed to explain the observed isotopic signatures. Here we show that the high degree of heterogeneity is not confined to the isotopes of the lithophile elements, but is also shown by the noblegas isotopes and noblegas interelement ratios, such as e.g. 3He/22NeM or 4He/40Ar*. 3He/4He, 21Ne/22Neextra and 40Ar/36Ar range from 7.3 to 9.3 RA, from 0.05 to 0.08, and from 346 to 37,400, respectively. Nevertheless, the majority of the Ne isotope data are clearly aligned along a single mixing line in the Ne-three-isotope diagram, represented by the equation 20Ne/22Ne=70.5 x 21Ne/22Ne + 7.782, with a slope distinctly different from that of the MORB line, indicating that the ultra-depleted material is characterised by a significantly more nucleogenic 21Ne/22Ne isotopy than the normal depleted mantle. We show, based on covariations between 3He/4He and 21Ne/22Neextra with 206Pb/204Pb and 178Hf/177Hf, that the ultra-depleted material erupted at this MAR segment was most likely produced by an ancient, deep melting event. This implies that isotopic heterogeneities in the upper mantle are not solely caused by the injection of enriched materials from deep-seated mantle plumes or by crustal recycling but may also be due to differences in the depth and degree of melting of upper mantle material within

Emission of terahertz (THz) electromagnetic radiation from heavily-doped (5 × 1018 cm-3) (100) and (111) InP bulk materials and nanoporous honeycomb membranes, irradiated with heavy noblegas (Kr and Xe) ions, is presented. Irradiating samples with Kr or Xe improves THz emission efficiency. For (111) samples, as for unirradiated samples, the irradiated porous structures generate more THz radiation than their bulk counterparts. On the other hand, in contrast to unirradiated (100) samples, the irradiated (100) samples show a decrease in THz emission with porosity. We attribute this behaviour to changes in the local electric field due to the combined effect of the irradiation and nanoporosity.

We present a detailed theoretical analysis of the noble-gas nuclear-spin relaxation due to the anisotropic magnetic-dipole hyperfine interaction between the noble-gas nucleus and alkali-metal valence electron vis à vis the already well-understood (spin-conserving) isotropic magnetic-dipole hyperfine interaction in alkali-metal-noble-gas systems. We find that, for all pairs in which the noblegas is not helium, the predicted spin-relaxation rate from the anisotropic interaction does not exceed 2.5% of the rate from the isotropic interaction, thereby not appreciably limiting the maximum noble-gas nuclear polarization attainable via spin-exchange collisions with polarized alkali-metal atoms. For alkali-metal-helium pairs, we predict that the anisotropic interaction has a slightly larger relative effect, perhaps limiting the nuclear polarization to ~95% of the electronic polarization in the Rb-3He system; however, our confidence in the helium results is limited by a lack of knowledge of the interatomic potentials necessary for the calculation.

Noblegas isotope composition in thermal groundwater provides information about crust-mantle interactions, in form of geotectonic activity, volcanism and advective heat transfer. The knowledge of the geothermal state of the crust is useful for the indication of thermal energy resources, which are of significant environmental and economic importance. In this study, groundwater samples were collected in Israel and Jordan in 2012, along the east and west sides of the central Dead Sea Transform. The helium isotope ratio, 3He/4He, is a well-established marker to discriminate three different geochemical reservoirs: Atmosphere, crust and mantle. The distinct isotope ratios in each reservoir make it possible to separate the total helium concentration in groundwater into mantle, crustal (radiogenic) and atmospheric components. The 3He/4He ratios of all sampled waters exceed the typical crustal ratio, indicating contributions of mantle-derived helium to the total helium concentration. Most of the samples contain less than 3% atmospheric helium, whereas the mantle-derived helium component ranges from 1% to 61%. In Israel, a clear trend is observed. Samples from the northern parts of the sampling area show higher 3He/4He ratios than samples from southern parts. These findings confirm Torfstein et al. [1], who analyzed thermal groundwaters from Israel. In our data from Jordan, however, no north-south trend is seen, but a local anomaly is observed in the area between the Dead Sea and the Sea of Galilee, with a 3He/4He ratio that is 5 times higher than the atmospheric 3He/4He ratio. Moreover, some samples from North Jordan exhibit only minor mantle contributions, compared to the samples from the north of Israel. Our results emphasize the importance of local faulting patterns, which enable a better transfer of mantle derived helium into the shallow crust. In addition to helium, the origin of CO2 in the water was examined. Measurements of δ13C suggest that CO2 originates from

The nuclear industry emissions of the four CTBT (Comprehensive Nuclear-Test-Ban Treaty) relevant radioxenon isotopes are unavoidably detected by the IMS along with possible treaty violations. Another civil source of radioxenon emissions which contributes to the global background is radiopharmaceutical production companies. To better understand the source terms of these background emissions, a joint project between HC, ANSTO, PNNL and CRL was formed to install real-time detection systems to support 135Xe, 133Xe, 131mXe and 133mXe measurements at the ANSTO and CRL 99Mo production facility stacks as well as the CANDU (CANada Deuterium Uranium) primary coolant monitoring system at CRL. At each site, high resolution gamma spectra were collected every 15 minutes using a HPGe detector to continuously monitor a bypass feed from the stack or CANDU primary coolant system as it passed through a sampling cell. HC also conducted atmospheric monitoring for radioxenon at approximately 200 km distant from CRL. A program was written to transfer each spectrum into a text file format suitable for the automatic gamma-spectra analysis platform and then email the file to a server. Once the email was received by the server, it was automatically analysed with the gamma-spectrum software UniSampo/Shaman to perform radionuclide identification and activity calculation for a large number of gamma-spectra in a short period of time (less than 10 seconds per spectrum). The results of nuclide activity together with other spectrum parameters were saved into the Linssi database. This database contains a large amount of radionuclide information which is a valuable resource for the analysis of radionuclide distribution within the noblegas fission product emissions. The results could be useful to identify the specific mechanisms of the activity release. The isotopic signatures of the various radioxenon species can be determined as a function of release time. Comparison of 133mXe and 133Xe activity

In the paper a novel non-dispersive infrared(IR) gasmonitor is described.It is based on the principle that certain gases absorb IR radiation at specific(and often unique) wavelengths.Conventional devices typically include several primary components:a broadband source, usually an incandescent filament,a rotating chopper shutter,a narrow-band filter,a sample tube and a detector. We have developed a number of IR light emitting diodes(LED) having narrow optical bandwidths and which can be intensity modulated by electrical means,for example InAsSbP(4.2 micron)LED.The IR LED can thus replace the thermal source,narrow-band filter and chopper assembly of the conventional IR gasmonitor,yielding a solid state,low- powered,compact and almost maintenance-free instrument with high sensitivity and stability and which free of the effects of mechanical vibration too. The detector used in the IR gasmonitor is the solid-state detector,such as PbS,PbSe, InSb,HgCdTe,TGS,LT and PZT detector etc. The different configuration of the IR gasmonitor is designed.For example,two-path version for measuring methane concentration by monitoring the 3.31 micron absorption band,it can eliminate the interference effects,such as to compensate for LED intensity changes caused by power and temperature variations,and for signal fluctuations due to changes in detector bias. we also have designed portable single-beam version without the sample tube.Its most primary advantage is very cheap(about cost USD 30 ).It measures carbon dioxide concentration by monitoring the 4.25 micron absorption band.Thought its precisions is low,it is used to control carbon dioxide concentration in the air in the green houses and plastic houses(there are about twenty millon one in the China).Because more carbon dioxide will increase the quanity of vegetable and flower production to a greatextent. It also is used in medical,sanitary and antiepidemic applications,such as hospital, store,hotel,cabin and ballroom etc. Key words

[1] Bedrock groundwater in alpine watersheds is poorly understood, mainly because of a scarcity of wells in alpine settings. Groundwater noblegas, age, and temperature data were collected from springs and wells with depths of 3-342 m in Handcart Gulch, an alpine watershed in Colorado. Temperature profiles indicate active groundwater circulation to a maximum depth (aquifer thickness) of about 200 m, or about 150 m below the water table. Dissolved noblegas data show unusually high excess air concentrations (>0.02 cm3 STP/g, ??Ne > 170%) in the bedrock, consistent with unusually large seasonal water table fluctuations (up to 50 m) observed in the upper part of the watershed. Apparent 3H/3He ages are positively correlated with sample depth and excess air concentrations. Integrated samples were collected from artesian bedrock wells near the trunk stream and are assumed to approximate flow-weighted samples reflecting bedrock aquifer mean residence times. Exponential mean ages for these integrated samples are remarkably consistent along the stream, four of five being from 8 to 11 years. The tracer data in combination with other hydrologic and geologic data support a relatively simple conceptual model of groundwater flow in the watershed in which (1) permeability is primarily a function of depth; (2) water table fluctuations increase with distance from the stream; and (3) recharge, aquifer thickness, and porosity are relatively uniform throughout the watershed in spite of the geological complexity of the Proterozoic crystalline rocks that underlie it. Copyright 2007 by the American Geophysical Union.

Bedrock groundwater in alpine watersheds is poorly understood, mainly because of a scarcity of wells in alpine settings. Groundwater noblegas, age, and temperature data were collected from springs and wells with depths of 3-342 m in Handcart Gulch, an alpine watershed in Colorado. Temperature profiles indicate active groundwater circulation to a maximum depth (aquifer thickness) of about 200 m, or about 150 m below the water table. Dissolved noblegas data show unusually high excess air concentrations (>0.02 cm3 STP/g, ΔNe > 170%) in the bedrock, consistent with unusually large seasonal water table fluctuations (up to 50 m) observed in the upper part of the watershed. Apparent 3H/3He ages are positively correlated with sample depth and excess air concentrations. Integrated samples were collected from artesian bedrock wells near the trunk stream and are assumed to approximate flow-weighted samples reflecting bedrock aquifer mean residence times. Exponential mean ages for these integrated samples are remarkably consistent along the stream, four of five being from 8 to 11 years. The tracer data in combination with other hydrologic and geologic data support a relatively simple conceptual model of groundwater flow in the watershed in which (1) permeability is primarily a function of depth; (2) water table fluctuations increase with distance from the stream; and (3) recharge, aquifer thickness, and porosity are relatively uniform throughout the watershed in spite of the geological complexity of the Proterozoic crystalline rocks that underlie it.

The existence of new interesting insertion compounds, HNgCS(+) (Ng = He-Xe), have been predicted theoretically through insertion of a noblegas atom into the thioformyl cation, HCS(+). Second-order Møller-Plesset perturbation theory (MP2), density functional theory (DFT), and coupled-cluster theory (CCSD(T)) based techniques have been used to explore the structure, energetics, charge distribution, and harmonic vibrational frequencies of these compounds. These predicted ions are found to be energetically stable with respect to all the possible 2-body and 3-body dissociation pathways, except the 2-body channel leading to the global minimum products (HCS(+) + Ng). Nevertheless, all these ions are found to be kinetically stable with a finite barrier height corresponding to their transition states, which are connected to their respective global minima products. The results obtained from charge distribution as well as atoms in molecules (AIM) analysis suggest that these ions can be best described as [HNg](+)CS. Strong covalent character in the H-Ng bond is supported by the high positive energy value corresponding to the 3-body dissociation pathways. Thus, it might be possible to prepare the HNgCS(+) ions in a glow discharge containing H2S, CO, and noblegas under cryogenic conditions through matrix isolation technique. PMID:24960593

A variety of processes have been considered possibly contributing the volatiles including noble gases to the atmospheres of the terrestrial planets (e.g., [1-3]). Special consideration has been given to the concept of accretion of volatile-rich materials by the forming planets. This might include infalling planetesimals and dust, and could include material from the outer asteroid belt, as well as cometary material from the outer solar system. Currently, the dominant source of extraterrestrial material accreted by the Earth is represented by micrometeorites (MMs) with sizes mostly in the 100-300 micron range [3, 4]). Their role has been assessed by [3], who conclude that accretion of early micrometeorites played a major role in the formation of the terrestrial atmosphere and oceans. We have therefore set out to investigate in more detail the inventory of noble gases in MMs. Here we summarize some of our results obtained on MMs collected in micrometeorite traps of the Transantarctic Mountains [5].

Stalagmites represent excellent multi-proxy paleoclimate archives as they cover long timescales and can be dated with high precision [e.g., 1]. The absolute temperature at which a stalagmite grew, can be deduced from the amounts of atmospheric noble gases dissolved in the stalagmite's fluid inclusion water (= noblegas temperature, NGT) [2-4]. We present technical advances towards more robust NGT determinations and also propose a new paleoclimate proxy, namely the stalagmite's water content, which is a "by-product" of NGT determination. Water contents and oxygen isotope records of two Holocene stalagmites from Socotra Island (Yemen) were found to vary systematically: progressively lighter oxygen is accompanied by decreasing water contents and vice versa. Via the oxygen isotope records [5] the stalagmites' water contents are linked to the amounts of precipitation on Socotra Island. High precipitation, i.e., high drip rates lead to homogeneous calcite growth with low porosity and therefore a small number of water-filled inclusions, i.e. low water contents. A reduction of drip water supply fosters irregular crystal growth with higher porosity, leading to higher water contents of the calcite (see also [6]). Therefore the stalagmites' water contents seem to record changes in drip water supply and, under favourable conditions, changes in regional precipitation. The current method to extract water and noble gases from stalagmite samples is experimentally challenging and subject to certain limitations (e.g., time-consuming sample preparation in a glove box, temperature restrictions for water extraction, and the often inadequate correction for air from residual air-filled inclusions [3, 4]). To overcome these limitations we have developed a new type of crusher directly attached to our noblegas line. It not only allows crushing and separating the samples into different grain size fractions in vacuo, but the separates can be individually heated to significantly higher

Santorini is one of the most famous active volcanoes of the world for its catastrophic explosive eruption that occurred during the Minoan civilization. Since then the Kameni eruptive centers that formed within the caldera erupted repeatedly until 1950. In 2011-2012 the volcano has been characterized by a seismic unrest, that was unprecedented at Santorini at least since the 1950 eruption, and that led to fear for an imminent eruption. Because more than 100,000 visitors are present on the island during the tourist season, and considering the eruptive potential of Santorini, it is crucial to evaluate the hazard of this volcano, which depends on the type of magma actually present in the volcanic system. With the aim to address this question, this research shows the first comparison between noble-gas isotope composition of the present fumarolic gases with that of fluid inclusions hosted in enclaves contained in the 1570 and 1925 AD dacitic magmas erupted at Nea Kameni. These enclaves are a portion of mafic magma batches that replenished the shallow chamber of the plumbing system hosting cooler and more silicic melts. Their Sr-Nd isotope ratios are quite similar to those measured in the host dacitic rocks, implying a common parental magma. Therefore, the analyzed enclaves may be considered representative of the historic magma erupted at Nea Kameni which could be still present in the volcano plumbing system feeding the crater fumaroles. The 3He/4He ratios of enclaves, once corrected for air contamination (3.1-3.6 Ra), partially overlap those of the gases (3.5-4.0 Ra) collected from Nea and Palea Kameni. The range of 3He/4He ratios (3.1-4.0 Ra) is appreciably lower than typical arc volcanoes (R/Ra ~7-8), implying that a contamination by 4He-rich fluids occurred either directly in the mantle and/or in the plumbing system. Comparison of 3He/4He and 4He/40Ar* ratios measured in enclaves with those of gases, as well as long-term monitoring of R/Ra in the latters, coherently

Electron loss and electron emission for grazing impact of noblegas atoms with energies in the keV domain are investigated via time-of-flight spectra recorded in coincidence with the number of emitted electrons. The data is analyzed in terms of computer simulations concerning the interaction of the fast atoms with the electron gas in the selvedge of the Al(1 1 1) surface. The interaction is approximated by binary collisions of the fast atoms with Fermi electrons of the conduction band and differential cross sections obtained for electron scattering from free atoms. For an effective number of collisions of about 50 the energy loss spectra are fairly well reproduced by our calculations. We show that for our conditions the shift of the energy spectra for the emission of an additional electron from the surface is close to the work function of the target.

A dual gas tracer experiment using sulfur hexafluoride (SF6) and an isotope of helium (3He) and measurements of dissolved noble gases was performed at the El Rio spreading grounds to examine gas transport and trapped air below an artificial recharge pond with a very high recharge rate (approximately 4 m day(-1)). Noblegas concentrations in the groundwater were greater than in surface water due to excess air formation showing that trapped air exists below the pond. Breakthrough curves of SF6 and 3He at two nearby production wells were very similar and suggest that nonequilibrium gas transfer was occurring between the percolating water and the trapped air. At one well screened between 50 and 90 m below ground, both tracers were detected after 5 days and reached a maximum at approximately 24 days. Despite the potential dilution caused by mixing within the production well, the maximum concentration was approximately 25% of the mean pond concentration. More than 50% of the SF6 recharged was recovered by the production wells during the 18 month long experiment. Our results demonstrate that at artificial recharge sites with high infiltration rates and moderately deep water tables, transport times between recharge locations and wells determined with gas tracer experiments are reliable. PMID:15984768

An analytic response theory formulation for the leading-order magnetic field-induced and field-dependent quadrupole splitting in nuclear magnetic resonance spectra is presented and demonstrated with first-principles calculations for {sup 21}Ne, {sup 36}Ar, and {sup 83}Kr in noblegas atoms. The case of molecules was studied for {sup 33}S in the sulphur hexafluoride molecule, as well as for {sup 47/49}Ti, {sup 91}Zr, and {sup 177,179}Hf in group(IV) tetrahalides. According to our calculations, the hitherto experimentally unknown field-induced quadrupole splitting in molecules rises to 10{sup 2} Hz for {sup 177,179}Hf nuclei in HfF{sub 4} and 10{sup 1} Hz for {sup 47/49}Ti in TiCl{sub 4}, and is hence of observable magnitude.

An apparatus and method for the generation of ultrabright multikilovolt x-rays from saturated amplification on noblegas transition arrays from hollow atom states is described. Conditions for x-ray amplification in this spectral region combine the production of cold, high-Z matter, with the direct, selective multiphoton excitation of hollow atoms from clusters using ultraviolet radiation and a nonlinear mode of confined, self-channeled propagation in plasmas. Data obtained is consistent with the presence of saturated amplification on several transition arrays of the hollow atom Xe(L) spectrum (.lambda..about.2.9 .ANG.). An estimate of the peak brightness achieved is .about.10.sup.29 .gamma..multidot.s.sup.-1.multidot.mm.sup.-2.multidot.mr.sup.-2 (0.1% Bandwidth).sup.-1, that is .about.10.sup.5 -fold higher than presently available synchotron technology.

A metastable argon laser operating at 912 nm has been demonstrated by optically pumping with a pulsed titanium sapphire laser to investigate the temporal dynamics of an Advanced NobleGas Laser (ANGL). Metastable argon concentrations on the order of 1011 cm-3 were maintained with the use of a radio frequency (RF) capacitively coupled discharge. The end-pumped laser produced output powers under 2 mW of average power with pulse lengths on the order of 100 ns. A comparison between empirical results and a four level laser model using longitudinally average pump and inter-cavity intensities is made. An alternative, highly-efficient method of argon metastable production for ANGL was explored using carbon nanotube (CNT) fibers.

Fluid origins in the sandstone-hosted Pb-Zn class of ore deposit have been investigated in three deposits from Scandinavia; Laisvall, Vassbo and Osen. The deposits studied are hosted by autochthonous Cambrian sandstones that preserve a near original structural relationship to the underlying Precambrian basement, enabling the role of basement interaction to be assessed. Mineral samples have been collected from across the paragenetic sequence: sphalerite, galena, pyrite, fluorite and barite, of impregnation and related joint-hosted mineralization. Fluid-inclusion halogen (Cl, Br and I) and noblegas isotope ( 40Ar, 36Ar, 84Kr) compositions were determined simultaneously by noblegas mass spectrometry of irradiated sample splits. Complementary He isotope analyses are obtained from nonirradiated splits of the same samples. 3He/ 4He values at Laisvall and Osen are highly radiogenic, 0.02 Ra, and the 4He/ 40Ar* ratio extends to values greater than the crustal production value of 5, characteristic of low-temperature crustal fluids. At Vassbo, a slightly elevated 3He/ 4He ratio of 0.1-0.3 Ra is compatible with a very minor mantle component (1%-4%) suggesting a distal source for the basinal brine-dominated fluid. Br/Cl molar ratios 3.2-8.2 × 10 -3 are greater than the present seawater value of 1.54 × 10 -3 and correspond with I/Cl molar ratios in the range 64-1600 × 10 -6. The upper limits of both the I/Cl and Br/Cl values are amongst the highest measured in crustal fluids. Together, the data indicate acquisition of salinity by the evaporation of seawater beyond the point of halite saturation and subsequent fluid interaction with I-rich organic matter in the subsurface. The data are compatible with the independent transport of sulfate and sulfide and indicate that fluids responsible for joint-hosted mineralization were distinct to those responsible for impregnation mineralization. All three deposits preserve fluids with 40Ar/ 36Ar in the range of 6,000-10,000 and fluid

An engineering evaluation has been initiated to investigate conceptual engineering methods for implementing a viable gas shield strategy in the Fusion Test Facility (FTF) target chamber. The employment of a low pressure noblegas in the target chamber to thermalize energetic helium ions prior to interaction with the wall could dramatically increase the useful life of the first wall in the FTF reactor1. For the purpose of providing flexibility, two target chamber configurations are addressed: a five meter radius sphere and a ten meter radius sphere. Experimental studies at Nike have indicated that a low pressure, ambient gas resident in the target chamber during laser pulsing does not appear to impair the ability of laser light from illuminating targets2. In addition, current investigations into delivering, maintaining, and processing low pressure gas appear to be viable with slight modification to current pumping and plasma exhaust processing technologies3,4. Employment of a gas fill solution for protecting the dry wall target chamber in the FTF may reduce, or possibly eliminate the need for other attenuating technologies designed for keeping He ions from implanting in first wall structures and components. The gas fill concept appears to provide an effective means of extending the life of the first wall while employing mostly commercial off the shelf (COTS) technologies. Although a gas fill configuration may provide a methodology for attenuating damage inflicted on chamber surfaces, issues associated with target injection need to be further analyzed to ensure that the gas fill concept is viable in the integrated FTF design5. In the proposed system, the ambient noblegas is heated via the energetic helium ions produced by target detonation. The gas is subsequently cooled by the chamber wall to approximately 800oC, removed from the chamber, and processed by the chamber gas processing system (CGPS). In an optimized scenario of the above stated concept, the chamber

Rising atmospheric carbon dioxide (CO2) concentrations are fueling anthropogenic climate change. Geologic sequestration of anthropogenic CO2 in depleted oil reservoirs is one option for reducing CO2 emissions to the atmosphere while enhancing oil recovery. In order to evaluate the feasibility of using enhanced oil recovery (EOR) sites in the United States for permanent CO2 storage, an active multi-stage miscible CO2 flooding project in the Permian Basin (North Ward Estes Field, near Wickett, Texas) was investigated. In addition, two major natural CO2 reservoirs in the southeastern Paradox Basin (McElmo Dome and Doe Canyon) were also investigated as they provide CO2 for EOR operations in the Permian Basin. Produced gas and water were collected from three different CO2 flooding phases (with different start dates) within the North Ward Estes Field to evaluate possible CO2 storage mechanisms and amounts of total CO2 retention. McElmo Dome and Doe Canyon were sampled for produced gas to determine the noblegas and stable isotope signature of the original injected EOR gas and to confirm the source of this naturally-occurring CO2. As expected, the natural CO2 produced from McElmo Dome and Doe Canyon is a mix of mantle and crustal sources. When comparing CO2 injection and production rates for the CO2 floods in the North Ward Estes Field, it appears that CO2 retention in the reservoir decreased over the course of the three injections, retaining 39%, 49% and 61% of the injected CO2 for the 2008, 2010, and 2013 projects, respectively, characteristic of maturing CO2 miscible flood projects. Noblegas isotopic composition of the injected and produced gas for the flood projects suggest no active fractionation, while δ13CCO2 values suggest no active CO2 dissolution into formation water, or mineralization. CO2 volumes capable of dissolving in residual formation fluids were also estimated along with the potential to store pure-phase supercritical CO2. Using a combination of

The possibility of the existence of a new series of neutral noblegas compound, FNgBS (where Ng = Ar, Kr, Xe), is explored theoretically through the insertion of a Ng atom into the fluoroborosulfide molecule (FBS). Second-order Møller-Plesset perturbation theory, density functional theory, and coupled cluster theory based methods have been employed to predict the structure, stability, harmonic vibrational frequencies, and charge distribution of FNgBS molecules. Through energetics study, it has been found that the molecules could dissociate into global minima products (Ng + FBS) on the respective singlet potential energy surface via a unimolecular dissociation channel; however, the sufficiently large activation energy barriers provide enough kinetic stability to the predicted molecules, which, in turn, prevent them from dissociating into the global minima products. Moreover, the FNgBS species are thermodynamically stable, owing to very high positive energies with respect to other two two-body dissociation channels, leading to FNg + BS and F(-) + NgBS(+), and two three-body dissociation channels, corresponding to the dissociation into F + Ng + BS and F(-) + Ng + BS(+). Furthermore, the Mulliken and NBO charge analysis together with the AIM results reveal that the Ng-B bond is more of covalent in nature, whereas the F-Ng bond is predominantly ionic in character. Thus, these compounds can be better represented as F(-)[NgBS](+). This fact is also supported by the detail analysis of bond length, bond dissociation energy, and stretching force constant values. All of the calculated results reported in this work clearly indicate that it might be possible to prepare and characterize the FNgBS molecules in cryogenic environment through matrix isolation technique by using a mixture of OCS/BF3 in the presence of large quantity of noblegas under suitable experimental conditions. PMID:25928588

The existence of noblegas containing protonated silicon monoxide complexes have been predicted theoretically through ab initio quantum chemical methods. The predicted HNgOSi(+) ions are obtained by insertion of a noblegas atom (Ng = He, Ne, Ar, Kr, and Xe) between the H and O atoms in SiOH(+) ion. The structural parameters, energetics, harmonic vibrational frequencies, and charge distributions have been analyzed by optimizing the minima and the transition state structures using second-order Møller-Plesset perturbation theory (MP2), density functional theory (DFT), and coupled-cluster theory (CCSD(T)) based techniques. The predicted HNgOSi(+) ions are found to be stable with respect to all possible 2-body and 3-body dissociation channels, except the dissociation path leading to the respective global minimum products. However, these ions are found to be kinetically stable with respect to the global minimum dissociation process as revealed from the finite barrier heights, which in turn can prevent the transformation of these metastable species to the global minimum products. Furthermore, the computed bond lengths, vibrational frequencies, and force constant values suggest that a strong covalent bond exists between the H and Ng atoms in HNgOSi(+) ions while the Ng and O atoms share a strong van der Waals kind of interaction. Charge distributions and bonding analysis indicate that HNgOSi(+) ions can be best represented as strong complexes between the [HNg](+) ions and OSi molecule. All the computational results suggest that the predicted species, HNgOSi(+), may be prepared and characterized by suitable experimental technique at cryogenic temperature. PMID:26501440

Noblegas isotopes, radionuclides, and chemical abundances were studied in the lunar meteorites MAC88104 and MAC88105 collected in the MacAlpine Hills area of Antarctica. The concentrations of the noblegas isotopes and the radionuclide activities in the two meteorites are essentially identical, proving that the two meteorites are paired. From {sup 40}K-{sup 40}Ar dating the authors obtain a gas retention age of 3,550 {plus minus} 400 Ma, typical for lunar surface material. Probably before breccia compaction the MAC88104/5 material resided for 630 {plus minus} 200 Ma at an average shielding depth of 85 g/cm{sup 2}, that is, about 50 cm below the lunar surface in the lunar regolith, as judged from the concentration of cosmic-ray produced Kr and Xe isotopes. Although this duration of lunar regolith residence is relatively long, MAC88104/5 represent immature regolith material: the concentration of solar wind implanted noble gases are two orders of magnitude lower than those in mature lunar soil. The {sup 40}Ar/{sup 36}Ar ratio of the trapped component is 5.7 {plus minus} 1.0, indicating an intermediate antiquity of the material; the authors estimate that the solar wind and lunar atmospheric particles were implanted about 2,000 Ma ago. The radionuclide activities allow a determination of the exposure history of the MAC88104/5 material. The duration of the Moon-Earth transfer was {much lt} 0.24 Ma. The exposure histories of the lunar meteorites discussed in this work indicate that at least two impact events are required for their ejection from the Moon. The authors first noblegas results for lunar meteorite Yamato-793274 show that it represents mature lunar regolith material with relatively high concentrations of solar wind implanted noblegas and a duration of several hundred million years of exposure to cosmic rays.

Brief analysis of design features and operational modes of Mayak PA industrial graphite-uranium reactors (PUGRs) is given. The above mentioned Mayak PA PUGRs determined the rates of releases of radioactive noble gases (RNG) from activation (41Ar) and fission (isotopes of Krypton and Xenon) through the vent stack of the reactor. Information is given on methods and results of experimental determination of RNG atmospheric releases for the period starting from 1965 till PUGRs decommissioning in 1987-1990. A calculation method for reconstruction of radioactive noblegas releases is proposed and justified. The results of reconstruction are given. It is shown that maximum rates of RNG releases from PUGRs high stacks were observed in the 1950s, when ordinary atmospheric air was used as a cover gas for the reactor graphite stacks and gas purification systems (flow-type gas holders) had not been installed yet.

We determined noblegas composition of minerals separated from mantle-derived xenoliths hosted by andesites in the active Avacha volcano, Kamchatka peninsula, Russia in order to better constrain the provenance and nature of fluids involved in partial melting and metasomatism in the mantle wedge. The lithospheric mantle beneath Avacha mainly consists of spinel harzburgites produced by high degrees of melt extraction. Data on coarse olivine separated from seven harzburgite xenoliths constrain fluid regime during flux melting in arc settings. Pyroxenes from two websterite veins cross-cutting the harzburgites characterize post-melting metasomatism by subduction-related melts or fluids. 3He/4He-ratios of 5.2 ± 0.6 to 8.1 ± 0.3 RA obtained on both olivines and pyroxenes overlap the highest values reported for volcanic rocks from Kamchatka and fall into the typical range of continental lithospheric mantle worldwide. This rules out significant contributions of slab-derived radiogenic 4He*. The highest 40Ar/36Ar ratios are 400; Ne and Xe isotope ratios are indistinguishable from those in the air. We consider the slab as the initial source of a major portion of these ‘atmospheric’ gases. Element composition of noble gases in olivine differs markedly from that in vein pyroxene indicating that the composition of the fluid phase involved in partial melting was distinct from that during metasomatism. In particular, the harzburgites and veins define distinct linear trends on plots of 3He/36Ar vs. 40Ar/36Ar and of 132Xe/36Ar vs. 40Ar/36Ar. Estimates of ‘mantle’ 132Xe/36Ar values by extrapolating 40Ar/36Ar to 40 000 yield unrealistically high values of 0.5-0.8 (olivine) and 4-5 (vein pyroxene) ruling out a simple two-component mixing of mantle and atmospheric noble gases. Rather a two-stage mixing process applies: (1) Changes in relative proportions of slab-derived element-fractionated atmospheric gases and ‘mantle’ produce two hybrid mixtures dominated by atmospheric

It has been shown that post detonation energetic helium ions can drastically reduce the useful life of the (dry) first wall of an IFE reactor due to the accumulation of implanted helium. For the purpose of attenuating energetic helium ions from interacting with first wall components in the Fusion Test Facility (FTF) target chamber, several concepts have been advanced. These include magnetic intervention (MI), deployment of a dynamically moving first wall, use of a sacrificial shroud, designing the target chamber large enough to mitigate the damage caused by He ions on the target chamber wall, and the use of a low pressure noblegas resident in the target chamber during pulse power operations. It is proposed that employing a low-pressure (~ 1 torr equivalent) noblegas in the target chamber will thermalize energetic helium ions prior to interaction with the wall. The principle benefit of this concept is the simplicity of the design and the utilization of (modified) existing technologies for pumping and processing the noble ambient gas. Although the gas load in the system would be increased over other proposed methods, the use of a "gas shield" may provide a cost effective method of greatly extending the first wall of the target chamber. An engineering study has been initiated to investigate conceptual engineering metmethods for implementing a viable gas shield strategy in the FTF.

The Idaho cobalt belt is a 60-km-long alignment of deposits composed of cobaltite, Co pyrite, chalcopyrite, and gold with anomalous Nb, Y, Be, and rare-earth elements (REEs) in a quartz-biotite-tourmaline gangue hosted in Mesoproterozoic metasedimentary rocks of the Lemhi Group. It is the largest cobalt resource in the United States with historic production from the Blackbird Mine. All of the deposits were deformed and metamorphosed to upper greenschist-lower amphibolite grade in the Cretaceous. They occur near a 1377 Ma anorogenic bimodal plutonic complex. The enhanced solubility of Fe, Co, Cu, and Au as chloride complexes together with gangue biotite rich in Fe and Cl and gangue quartz containing hypersaline inclusions allows that hot saline fluids were involved. The isotopes of B in gangue tourmaline are suggestive of a marine source, whereas those of Pb in ore suggest a U ± Th-enriched source. The ore and gangue minerals in this belt may have trapped components in fluid inclusions that are distinct from those in post-ore minerals and metamorphic minerals. Such components can potentially be identified and distinguished by their relative abundances in contrasting samples. Therefore, we obtained samples of Co and Cu sulfides, gangue quartz, biotite, and tourmaline and post-ore quartz veins as well as Cretaceous metamorphic garnet and determined the gas, noblegas isotope, and ion ratios of fluid inclusion extracts by mass spectrometry and ion chromatography. The most abundant gases present in extracts from each sample type are biased toward the gas-rich population of inclusions trapped during maximum burial and metamorphism. All have CO2/CH4 and N2/Ar ratios of evolved crustal fluids, and many yield a range of H2-CH4-CO2-H2S equilibration temperatures consistent with the metamorphic grade. Cretaceous garnet and post-ore minerals have high RH and RS values suggestive of reduced sulfidic conditions. Most extracts have anomalous 4He produced by decay of U and Th and

Noblegas, petrological, and chemical studies made on grain-size separates from lunar regolith breccia 14318 demonstrate that the noble gases are organized into two functional components, volume-correlated and surface-correlated. As in regolith breccia 14301, volume-correlated xenon in 14318 is primarily spallation-derived and the surface-correlated component contains not only solar wind xenon but also significant amounts of ''parentless' xenon from the fission of now extinct /sup 244/Pu and the decay of now extinct /sup 129/I (''parentless'' means the daughter products were incorporated onto grain surfaces following decay of the parent nuclide elsewhere). The ratio of /sup 129/Xe//sup 136/Xe in the total surface-correlated parentless component, as identified in grain-size analysis, is substantially higher than in the least tightly bound parentless component identified in stepwise heating analyses, confirming the trend seen in 14301. If the order of release of gases in stepwise heating is related to the order of incorporation in the simplest way (first in, last out), incorporation of these grain-surface components was probably time-ordered. The /sup 129/Xe//sup 136/Xe ratio in each identifiable parentless component would then be characteristic of the xenon available for surface adsorption at the particular time of acquisition. Continuous variations in this ratio further suggest that incorporation of the parentless xenon was closely coupled with production. Such observations provide the basis for a new chronometer from which we conclude that acquisition of parentless xenon was an ongoing process spanning at least 90 m.y., beginning no more than 44 +- 34 m.y. after the formation of the most meteorites and possibly predating xenon acquisition for the earth.

We address the problem of the sequestration of Ar, Kr, and Xe by H{sub 3}{sup +} in the gas-phase conditions encountered during the cooling of protoplanetary disks when H{sub 3}{sup +} is competing with other species present in the same environment. Using high-level ab initio simulations, we try to quantify other sequestration possibilities involving He, H{sub 5}{sup +}, H{sub 2}O, and H{sub 3}O{sup +} present in the protosolar nebula. Apart from the fact that H{sub 3}{sup +} complexes formed with heavy noble gases are found to be by far much more stable than those formed with He or H{sub 2}O, we show that H{sub 2}D{sup +} and H{sub 3}O{sup +}, both products of the reactions of H{sub 3}{sup +} with HD and H{sub 2}O, can also be efficient trapping agents for Ar, Kr, and Xe. Meanwhile, the abundance profile of H{sub 3}{sup +} in the outer part of the nebula is revisited with the use of an evolutionary accretion disk model that allows us to investigate the possibility that heavy noble gases can be sequestered by H{sub 3}{sup +} at earlier epochs than those corresponding to their trapping in planetesimals. We find that H{sub 3}{sup +} might be abundant enough in the outer protosolar nebula to trap Xe and Kr prior their condensation epochs, implying that their abundances should be solar in Saturn's current atmosphere and below the observational limit in Titan. The same scenario predicts that comets formed at high heliocentric distances should also be depleted in Kr and Xe. In situ measurements, such as those planed with the Rosetta mission on 67P/Churyumov-Gerasimenko, will be critical to check the validity of our hypotheses.

Chondrites are considered as the building rocks of the Earth as they represent remnants of the protoplanetary accretion stage. Among all chondritic classes, heavy noble gases are mainly concentrated in phase Q [1] hence it represents a likely primordial composition of the Earth. This is supported by the observation of [2] who detected this peculiar composition in CO2 well gases thanks to Kr isotopes. As CO2 well gases are supposed to derive from the same reservoir as MORBs [3], this signature should be observed in MORBs and OIBs as well. In this perspective, we will present analyses performed by mass spectrometry of MORBs and OIBs samples for all noble gases. Preliminary results are quite promising as the same trend seems to appear into OIB and MORB data for Kr isotopes. However, our analyses show that this primordial composition isn't displayed for stable isotopes of Xe as already observed by [4-5] and remains a trace in the mantle signature, which appears at first sight atmospheric. We thus propose that subduction of atmospheric noble gases has gradually covered this meteoritic imprint. In order to test this scenario, we will present a modelling performed for Ar and Xe in three distinct reservoirs: mantle, atmosphere and continental crust. The mantle is considered as homogenized by convection and similar to the MORB reservoir. Its degasing is divided in two stages: a massive early degasing followed by a decreasing one describing the cooling of the Earth's interior. Extraction of parent elements from the mantle to the continental crust is also taken into account as well as distillation of atmospheric Xe needed to explain the missing Xe paradox and the present Xe isotopic signature of the atmosphere. Finally, subduction of noble gases is assimilated to simple incorporation into the mantle of elementally fractionated air, enriched in heavy noble gases as supported by [6]. Thus, we show that starting with a chondritic composition, the present mantle composition can

The model of the geothermal system in which deep circulating groundwater containing noble gases, at air saturated water concentrations, mixes with hot fluids of mantle origin at depth, is extended to include the effect of interaction of the ascending fluid with both solid and gaseous phases of basement (or other) rocks en route to the surface. It is demonstrated that this interaction is responsible for most of the CO{sub 2} in the Taupo Volcanic Zone (TVZ) geothermal systems. It is proposed that the modeling of this interaction might be accomplished by techniques similar to those used for the understanding of the oxygen isotope shift found in geothermal systems. The water rock interaction experiments of Ellis and Mahon (1964, 1967) provides some data on the kinetic rates for B and Cl dissolution from rocks likely to be encountered in the geothermal system, but further information on the behavior of B may be needed. If these problems can be overcome this modeling technique has promise for the estimation of the recharge of geothermal systems and hence the sustainability of these systems.

Ground-water samples were collected from 56 locations throughout the Espanola Basin and analyzed for general chemistry (major ions and trace elements), carbon isotopes (delta 13C and 14C activity) in dissolved inorganic carbon, noble gases (He, Ne, Ar, Kr, Xe, and 3He/4He ratio), and tritium. Temperature profiles were measured at six locations in the southeastern part of the basin. Temperature profiles suggest that ground water generally becomes warmer with distance from the mountains and that most ground-water flow occurs at depths 50 years old, consistent with the 14C ages. Terrigenic He (Heterr) concentrations in ground water are high (log Delta Heterr of 2 to 5) throughout much of the basin. High Heterr concentrations are probably caused by in situ production in the Tesuque Formation from locally high concentrations of U-bearing minerals (Northeast zone only), or by upward diffusive/advective transport of crustal- and mantle-sourced He possibly enhanced by basement piercing faults, or by both. The 3He/4He ratio of Heterr (Rterr) is commonly high (Rterr/Ra of 0.3-2.0, where Ra is the 3He/4He ratio in air) suggesting that Espanola Basin ground water commonly contains mantle-sourced He. The 3He/4He ratio of Heterr is generally the highest in the western and southern parts of the basin, closest to the western border fault system and the Quaternary to Miocene volcanics of the Jemez Mountains and Cerros del Rio.

Key characteristics of California groundwater systems related to aquifer vulnerability, sustainability, recharge locations and mechanisms, and anthropogenic impact on recharge are revealed in a spatial geostatistical analysis of a unique data set of tritium, noble gases and other isotopic analyses unprecedented in size at nearly 4000 samples. The correlation length of key groundwater residence time parameters varies between tens of kilometers ((3)H; age) to the order of a hundred kilometers ((4)Heter; (14)C; (3)Hetrit). The correlation length of parameters related to climate, topography and atmospheric processes is on the order of several hundred kilometers (recharge temperature; δ(18)O). Young groundwater ages that highlight regional recharge areas are located in the eastern San Joaquin Valley, in the southern Santa Clara Valley Basin, in the upper LA basin and along unlined canals carrying Colorado River water, showing that much of the recent recharge in central and southern California is dominated by river recharge and managed aquifer recharge. Modern groundwater is found in wells with the top open intervals below 60 m depth in the southeastern San Joaquin Valley, Santa Clara Valley and Los Angeles basin, as the result of intensive pumping and/or managed aquifer recharge operations. PMID:26803267

Gas holdup tests performed in a small-scale mechanically-agitated mixing system at the Savannah River National Laboratory (SRNL) were reported in 2006. The tests were for a simulant of waste from the Hanford Tank 241-AZ-101 and featured additions of DOW Corning Q2-3183A Antifoam agent. Results indicated that this antifoam agent (AFA) increased gas holdup in the waste simulant by about a factor of four and, counter intuitively, that the holdup increased as the simulant shear strength decreased (apparent viscosity decreased). These results raised questions about how the AFA might affect gas holdup in Hanford Waste Treatment and Immobilization Plant (WTP) vessels mixed by air sparging and pulse-jet mixers (PJMs). And whether the WTP air supply system being designed would have the capacity to handle a demand for increased airflow to operate the sparger-PJM mixing systems should the AFA increase retention of the radiochemically generated flammable gases in the waste by making the gas bubbles smaller and less mobile, or decrease the size of sparger bubbles making them mix less effectively for a given airflow rate. A new testing program was developed to assess the potential effects of adding the DOW Corning Q2-3183A AFA to WTP waste streams by first confirming the results of the work reported in 2006 by Stewart et al. and then determining if the AFA in fact causes such increased gas holdup in a prototypic sparger-PJM mixing system, or if the increased holdup is just a feature of the small-scale agitation system. Other elements of the new program include evaluating effects other variables could have on gas holdup in systems with AFA additions such as catalysis from trace noble metals in the waste, determining mass transfer coefficients for the AZ-101 waste simulant, and determining whether other AFA compositions such as Dow Corning 1520-US could also increase gas holdup in Hanford waste. This new testing program was split into two investigations, prototypic sparger

We report argon (Ar) noblegas, Ar-Ar ages and halogen abundances (Cl, Br, I) of Martian nakhlites Nakhla, NWA 998 and MIL 03346 to determine the presence of Martian hydrous fluids and weathering products. Neutron-irradiated samples were either crushed and step-heated (Nakhla only), or simply step-heated using a laser or furnace, and analysed for noble gases using an extension of the 40Ar-39Ar technique to determine halogen abundances. The data obtained provide the first isotopic evidence for a trapped fluid that is Cl-rich, has a strong correlation with 40ArXS (40ArXS = 40Armeasured - 40Arradiogenic) and displays 40ArXS/36Ar of ˜1000 - consistent with the Martian atmosphere. This component was released predominantly in the low temperature and crush experiments, which may suggest a fluid inclusion host. For the halogens, we observe similar Br/Cl and I/Cl ratios between the nakhlites and terrestrial reservoirs, which is surprising given the absence of crustal recycling, organic matter and frequent fluid activity on Mars. In particular, Br/Cl ratios in our Nakhla samples (especially olivine) are consistent with previously analysed Martian weathering products, and both low temperature and crush analyses show a similar trend to the evaporation of seawater. This may indicate that surface brines play an important role on Mars and on halogen assemblages within Martian meteorites and rocks. Elevated I/Cl ratios in the low temperature NWA 998 and MIL 03346 releases may relate to in situ terrestrial contamination, though we are unable to distinguish between low temperature terrestrial or Martian components. Whilst estimates of the amount of water present based on the 36Ar concentrations are too high to be explained by a fluid component alone, they are consistent with a mixed-phase inclusion (gas and fluid) or with shock-implanted Martian atmospheric argon. The observed fluid is dilute (low salinity, but high Br/Cl and I/Cl ratios), contains a Martian atmospheric component

Convergent margin processes play an important but poorly understood role in the distribution of terrestrial volatile species. For example, subduction processes filter volatiles from the subducting package, thereby restricting their return to the mantle. In addition, once extracted from the downgoing slab, volatiles become an essential component in the petrogenesis of island arc magmas. The noble gases, with their systematic variation in physical properties and diversity of radiogenic isotopes, should carry a uniquely valuable record of these processes. However, thus far studies of noble gases in arc volcanics have achieved only limited success in this regard. Subduction-related lavas and geothermal fluids carry (3)He/(4)He ratios equal to or slightly lower than those found in the depleted upper mantle source of mid-ocean ridge basalts. Apparently slab-derived helium (which should have (3)He/(4)He much less than MORB) is extensively diluted by MORB-like helium from the mantle wedge, making it difficult to use helium as a tracer of convergent margin processes. Interpretation of the heavier noble gases (Ne-Ar-Kr-Xe) in arc lavas has also proven difficult, because the lavas carry low noblegas concentrations and hence are subject to pervasive atmospheric contamination. The low noblegas concentrations may be a consequence of degassing in the high level magma chambers characteristic of arc stratovolcanos. We have recently initiated a project to better constrain the behavior of volatiles in subduction zones through geochemical studies of the tectonically unusual volcanoes of the Tabar-Lihir-Tanga-Feni (TLTF) arc in the Bismarck Archipelago, Papua New Guinea.

Convergent margin processes play an important but poorly understood role in the distribution of terrestrial volatile species. For example, subduction processes filter volatiles from the subducting package, thereby restricting their return to the mantle. In addition, once extracted from the downgoing slab, volatiles become an essential component in the petrogenesis of island arc magmas. The noble gases, with their systematic variation in physical properties and diversity of radiogenic isotopes, should carry a uniquely valuable record of these processes. However, thus far studies of noble gases in arc volcanics have achieved only limited success in this regard. Subduction-related lavas and geothermal fluids carry (3)He/(4)He ratios equal to or slightly lower than those found in the depleted upper mantle source of mid-ocean ridge basalts. Apparently slab-derived helium (which should have (3)He/(4)He much less than MORB) is extensively diluted by MORB-like helium from the mantle wedge, making it difficult to use helium as a tracer of convergent margin processes. Interpretation of the heavier noble gases (Ne-Ar-Kr-Xe) in arc lavas has also proven difficult, because the lavas carry low noblegas concentrations and hence are subject to pervasive atmospheric contamination. The low noblegas concentrations may be a consequence of degassing in the high level magma chambers characteristic of arc stratovolcanos. We have recently initiated a project to better constrain the behavior of volatiles in subduction zones through geochemical studies of the tectonically unusual volcanoes of the Tabar-Lihir-Tanga-Feni (TLTF) arc in the Bismarck Archipelago, Papua New Guinea.

The diffusive and bubble-mediated components of air-sea gas exchange can be quantified separately using time-series measurements of a suite of dissolved inert gases. We have evaluated the performance of four published air-sea gas exchange parameterizations using a five-day time-series of dissolved He, Ne, Ar, Kr, and Xe concentration in Monterey Bay, CA. We constructed a vertical model including surface air-sea gas exchange and vertical diffusion. Diffusivity was measured throughout the cruise from profiles of turbulent microstructure. We corrected the mixed layer gas concentrations for an upwelling event that occurred partway through the cruise. All tested parameterizations gave similar results for Ar, Kr, and Xe; their air-sea fluxes were dominated by diffusive gas exchange during our study. For He and Ne, which are less soluble, and therefore more sensitive to differences in the treatment of bubble-mediated exchange, the parameterizations gave widely different results with respect to the net gas exchange flux and the bubble flux. This study demonstrates the value of using a suite of inert gases, especially the lower solubility ones, to parameterize air-sea gas exchange.

The density functional version of symmetry-adapted perturbation theory, SAPT(DFT), is a computationally efficient method for calculating intermolecular interaction energies. We evaluate its accuracy by comparison with experimentally determined noblegas interaction potentials and sublimation enthalpies, most of which have not been previously calculated using this method. In order to compare the results with wavefunction methods, we also calculate these quantities using MP2 and, for noblegas dimers, using CCSD(T). For the crystal lattice energy calculations, we include corrections to the dispersion, electrostatic, and induction energies that account for the finite interaction distance cutoff and higher-order induction contributions. Overall, the energy values extrapolated to the complete basis set limit show that SAPT(DFT) achieves significantly better agreement with experiment than MP2. PMID:23060262

The McMurdo Dry Valleys (MDV), Antarctica, is the largest ice-free region on Antarctica. Lake Vanda, located in central Wright Valley, is the deepest lake among the MDV lakes. It has a relatively fresh water layer above 50 m with a hypersaline calcium-chloride brine below (50-72 m). The Onyx River is the only stream input into Lake Vanda. It flows westward from the coastal Lower Wright Glacier and discharges into Lake Vanda. Suggested by the published literature and this study, there has been and may still be groundwater input into Lake Vanda. Stable isotopes, major ions, and noblegas data from this study coupled with previously published data indicate that the bottom waters of Lake Vanda have had significant contributions from a deep groundwater system. The dissolved gas of the bottom waters of Lake Vanda display solubility concentrations rather than the Ar-enriched dissolved gas seen in the Taylor Valley lakes (such as Lake Bonney). The isotopic data indicate that the bottom calcium-chloride-brine of Lake Vanda has undergone very little evaporation. The calcium-chloride chemistry of the groundwater that discharges into Lake Vanda most likely results from the chemical weathering and dissolution of cryogenic evaporites (antarcticite and gypsum) within the glacial sediments of Wright Valley. The high calcium concentrations of the brine have caused gypsum to precipitate on the lake bottom. Our work also supports previous physical and chemical observations suggesting that the upper portion actively circulates and the hypersaline bottom layer does not. The helium and calcium chloride values are concentrated at the bottom, with a very narrow transition layer between it and the above fresh water. If the freshwater layer did not actively circulate, then diffusion over time would have caused the helium and calcium chloride to slowly permeate upwards through the water column.

The absorption of light during atomic collisions is treated by coupling electronic excitations, treated quantum mechanically, to the motion of the nuclei described within a short de Broglie wavelength approximation, using a density matrix approach. The time-dependent electric dipole of the system provides the intensity of light absorption in a treatment valid for transient phenomena, and the Fourier transform of time-dependent intensities gives absorption spectra that are very sensitive to details of the interaction potentials of excited diatomic states. We consider several sets of atomic expansion functions and atomic pseudopotentials, and introduce new parametrizations to provide light absorption spectra in good agreement with experimentally measured and ab initio calculated spectra. To this end, we describe the electronic excitation of the valence electron of excited alkali atoms in collisions with noblegas atoms with a procedure that combines l-dependent atomic pseudopotentials, including two- and three-body polarization terms, and a treatment of the dynamics based on the eikonal approximation of atomic motions and time-dependent molecular orbitals. We present results for the collision induced absorption spectra in the Li-He system at 720 K, which display both atomic and molecular transition intensities. PMID:17059261

Diffusion of heavy noblegas atoms in irradiation damaged single crystalline silicon carbide and the thermal etching of it is investigated at temperatures of 1300 °C and 1400 °C. For this purpose 360 keV krypton and xenon ions were implanted in commercial 6H-SiC wafers at 600 °C, which is far above the critical amorphization temperature of the target material. Width broadening of the implantation profiles and the retention of krypton and xenon during isothermal annealing was determined by RBS-analysis, whilst damage profiles were simultaneously obtained by α-particle channelling. No diffusion and no loss of the implanted species is detected in the implanted samples after isothermal annealing for 40 h at 1400 °C. However, thermal etching of the target material is observed at both annealing temperatures and leads at 1400 °C to a significant shift of the implantation profile towards the surface due to sublimation. RBS analysis shows that this occurs mainly during the initial stage of isothermal annealing, while surface loss during prolonged annealing is minimal. The resulting topographical modification of the surface during annealing was studied by scanning electron and atomic force microscopy. It indicates that the observed phenomenon is due to a relatively strong dependence of thermal etching on the defect density in the surface region, while the evolving surface roughness seems not to play a decisive role.

A promising technique for runaway electron (RE) mitigation in large-tokamak disruptions is the injection of compact toroid (CT) plasmas of high atomic number. With sufficient kinetic energy density, high-Z CTs can reach the tokamak magnetic axis where RE effects are strongest. At CT velocities of 100 km/s or more, penetration to the axis occurs on a sub-millisecond time scale. In addition to reducing avalanche RE production by collisions, high-Z CTs can cool RE by bremsstrahung effects. From theoretical calculations, using Xe ions, bremsstrahlung cooling exceeds the effect of collisions at RE energy above about 10 MeV, a value expected to be well exceeded in large tokamaks. Past experiments on the CTIX compact-toroid injector have demonstrated increased CT mass using snowplow accretion of puffed noblegas by an initial hydrogenic CT. These experiments will be continued using a higher ratio of accreted high-Z plasma to H plasma, to maximize CT kinetic energy density. Results will be compared with a 1D model using external circuit effects, coaxial railgun kinetics, and ionization. The model will be used to predict performance of CT injectors of greater energy, suitable for RE suppression on mid-sized tokamaks.

Theory has predicted oscillations in the photoionization cross section of various atoms trapped in C60. Most of the studies however modeled the confining shell by a simplistic one-active-electron potential. We recently established a method that treats the C60 electrons in a sophisticated multi-electron frame based on the density functional theory [1]. Using this method, we perform calculations for noblegas atoms in C60. In the past, the free C60 photo cross section, which also shows oscillations, was analyzed by a Fourier-transform technique to determine the origin of the oscillation [2] and its dependence on the electron's rotational motion [3]. In the present work, we employ the Fourier analysis to unravel the interplay between specific ionization modes that induces oscillations in the cross section of a confined atom. The quality of oscillations is found to strongly differ from the outermost to an inner subshell. [1] Madjet et al., J. Phys. B 41, 105101 (2008); [2] Ruedel et al., Phys. Rev. Letts. 89, 125503 (2002); [3] McCune et al., J. Phys. B FTC 41, 201003 (2008).

We present a genetic algorithm based investigation of structural fragmentation in dicationic noblegas clusters, Arn+2, Krn+2, and Xen+2, where n denotes the size of the cluster. Dications are predicted to be stable above a threshold size of the cluster when positive charges are assumed to remain localized on two noblegas atoms and the Lennard-Jones potential along with bare Coulomb and ion-induced dipole interactions are taken into account for describing the potential energy surface. Our cutoff values are close to those obtained experimentally [P. Scheier and T. D. Mark, J. Chem. Phys. 11, 3056 (1987)] and theoretically [J. G. Gay and B. J. Berne, Phys. Rev. Lett. 49, 194 (1982)]. When the charges are allowed to be equally distributed over four noblegas atoms in the cluster and the nonpolarization interaction terms are allowed to remain unchanged, our method successfully identifies the size threshold for stability as well as the nature of the channels of dissociation as function of cluster size. In Arn2+, for example, fissionlike fragmentation is predicted for n =55 while for n =43, the predicted outcome is nonfission fragmentation in complete agreement with earlier work [Golberg et al., J. Chem. Phys. 100, 8277 (1994)].

In this paper, we try to demonstrate that how many helium, neon and argon atoms can be trapped into fullerene cages until the pressure becomes large enough to break the C80 and Si80 frameworks. The maximum number of helium, neon and argon atoms which can be encapsulated into C80 fullerene, is found with 46, 24 and 10 atoms respectively. Having investigated the mechanism of C80 opening, we found that if the number of helium and argon atoms reaches to 50 and 12 respectively, the C-C bonds of C80 are broken and the gas molecules escaped from the fullerene cage. The final optimization geometries of latter complexes are similar to the shopping cart. Therefore, this appearance is named as molecular cart. Moreover, the maximum capacity of Si80 fullerene for encapsulated noblegas atoms is found 95, 56 and 22 for helium, neon and argon atoms correspondingly. It is worth highlighting that the new phenomenon of trapping argon atoms into Si80 cage is observed, when a Si atom randomly added to the center of Ar19@Si80 structures. In this case, the Si-Si bonds of Si80 are broken and two argon atoms will escape from the cage. After that, the framework rebuilds its structure like the initial one. This phenomenon is introduced as molecular cesarean section. The estimated internal pressure of Ng atoms trapped into the fullerene cages is also investigated. Results show that the maximum calculated internal pressure is related to He46@C80 and He95@Si80 structures with 212.3 and 144.1GPa respectively. PMID:25259413

The thermal oxidation of alloy nanoparticles (NPs) composed of nickel and a noble metal was investigated by high-resolution electron microscopic observations of the NPs oxidized in a gas phase under different oxidation conditions. When Ni0.8Au0.2 NPs were heated with oxygen from room temperature, oxidation progressed to form Au-NiO core-shell structures, however, the Au core spilled out by breaking the NiO shell at high temperatures. In contrast, when the alloy NPs were subjected to rapid thermal oxidation, which was enabled by heating the NPs at high temperatures (≥500 °C) and then abruptly exposed to oxygen, oxidation advanced anisotropically such that a NiO island protruded and built up to form a NiO nanorod. This resulted in the formation of Au-tipped NiO nanorods in which a hemispherical Au tip bonded to a NiO nanorod via a Au {111}/NiO{100} interface. We found that the relative sizes of Au and NiO in Au-tipped NiO nanorods were easily and widely controlled by changing the Au mole fraction (0.05-0.8) of the alloy NPs. Similarly, rapid thermal oxidation of Ni-Pt NPs generated Pt-tipped NiO nanorods in which a spherical Pt tip was half-embedded in a NiO nanorod. The present gas-phase approach has great potential for fabricating functional asymmetric hybrid nanostructures in clean conditions.

Discusses three types of sensors; pressure, gas detection, and relative humidity. Explains their use for laboratory measurements of gas pressure and detection of specific gaseous species. Shows diagrams of devices and circuits along with examples and applications including microcomputer interfacing. (RT)

We report the results of an accurate measurement of optical oscillator strengths of the prominent resonance lines of He, Ne, Ar and Kr in the vacuum ultraviolet. To measure the oscillator strength of a resonance line we make use of the absorption of the resonance radiation as it passes through the gas to a detector. The transmission of this radiation through a layer of gas of finite thickness is measured as a function of the number density of the gas. The transmission function is fitted to this data to obtain the absorption oscillator strength. The accuracy of the present measurements ranges from 2.5% to 4% and is reflected in the uncertainties presented below. The results are for He I (58.4 nm) 0.2683 +/- 0.0075 (2.8%), He I (53.7 nm) 0.0717 +/- 0.0024 (3.4%), Ne I (74.4 nm) 0.01017 +/- 0.00030 (2.9%), Ne I (73.6 nm) 0.1369 +/- 0.0035 (2.6%), Ar I (106.7 nm) 0.0616 +/- 0.0021 (3.4%), Ar I (104.8 nm) 0.2297 +/- 0.0093 (4.0%), Kr I (123.6 nm) 0.1751 +/- 0.0049 (2.8%) and Kr I (116.5 nm) 0.1496 +/- 0.0038 (2.5%).

The applications of low-temperature plasma are not only confined to decontamination and sterilization but are also found in the medical field in terms of wound and skin treatment. For the improvement of already established and also for new plasma techniques, in-depth knowledge on the interactions between plasma and microorganism is essential. In an initial study, the interaction between growing Bacillus subtilis and argon plasma was investigated by using a growth chamber system suitable for low-temperature gas plasma treatment of bacteria in liquid medium. In this follow-up investigation, a second kind of plasma treatment-namely air plasma-was applied. With combined proteomic and transcriptomic analyses, we were able to investigate the plasma-specific stress response of B. subtilis toward not only argon but also air plasma. Besides an overlap of cellular responses due to both argon and air plasma treatment (DNA damage and oxidative stress), a variety of gas-dependent cellular responses such as growth retardation and morphological changes were observed. Only argon plasma treatments lead to a phosphate starvation response whereas air plasma induced the tryptophan operon implying damage by photooxidation. Biological findings were supported by the detection of reactive plasma species by optical emission spectroscopy and Fourier transformed infrared spectroscopy measurements. PMID:23794223

Identifying the mechanism by which the injected CO2 is stored in underground reservoirs is a key challenge for carbon sequestration. Developing tracing tools that are universally deployable will increase confidence that CO2 remains safely stored. CO2 has been injected into the Cranfield enhanced oil recovery (EOR) field (MS, USA) since 2008 and significant amount of CO2 has remained (stored) in the reservoir. Noble gases (He, Ne, Ar, Kr, Xe) are present as minor natural components in the injected CO2. He, Ne and Ar previously have been shown to be powerful tracers of the CO2 injected in the field (Györe et al., 2015). It also has been implied that interaction with the formation water might have been responsible for the observed CO2 loss. Here we will present work, which examines the role of reservoir fluids as a CO2 sink by examining non-radiogenic noblegas isotopes (20Ne, 36Ar, 84Kr, 132Xe). Gas samples from injection and production wells were taken 18 and 45 months after the start of injection. We will show that the fractionation of noble gases relative to Ar is consistent with the different degrees of CO2 - fluid interaction in the individual samples. The early injection samples indicate that the CO2 injected is in contact with the formation water. The spatial distribution of the data reveal significant heterogeneity in the reservoir with some wells exhibiting a relatively free flow path, where little formation water is contacted. Significantly, in the samples, where CO2 loss has been previously identified show active and ongoing contact. Data from the later stage of the injection shows that the CO2 - oil interaction has became more important than the CO2 - formation water interaction in controlling the noblegas fingerprint. This potentially provides a means to estimate the oil displacement efficiency. This dataset is a demonstration that noble gases can resolve CO2 storage mechanisms and its interaction with the reservoir fluids with high resolution

We demonstrate through extensive first-principles time-dependent density functional calculations that attractive van der Waals interaction between closed-shell atoms can be enhanced by light with constant spatial intensity. We illustrate this general phenomenon for a He dimer as a prototypical case of complex van der Waals interactions and show that when excited by light with a frequency close to the 1s → 2p He-atomic transition, an attractive force larger than 7 pN is produced. This force gain is manifested as a larger acceleration of He-He contraction under an optical field. The concerted dynamical motions of the He atoms together with polarity switching of the charge-induced dipole cause the contraction of the dimer. These findings are relevant for the photo-induced control of weakly bonded molecular species, either in gas phase or in solution.

The Thermo Scientific HELIX-platform Split Flight Tube (HELIX-SFT) noblegas mass spectrometer is specifically designed for simultaneous collection of helium isotopes. The high mass spur houses a switchable 1011 - 1012 Ω resistor Faraday cup and the low mass spur a digital pulse-counting secondary electron multiplier (SEM). We have acquired the HELIX-SFT with the specific intention to measure argon isotopes for 40Ar/39Ar geochronology. This contribution will discuss preliminary performance (resolution, reproducibility, precision etc.) with respect to measuring argon isotope ratios for 40Ar/39Ar dating of geological materials. We anticipate the greatest impact for 40Ar/39Ar dating will be increased accuracy and precision, especially as we approach the techniques younger limit. Working with Thermo Scientific we have subtly modified the source, alpha and collector slits of the HELIX-SFT mass spectrometer to improve its resolution for resolving isobaric interferences at masses 36 to 40. The enhanced performance will allow for accurate and precise measurement of argon isotopes. Preliminary investigations show that we can obtain a valley resolution of >700 and >1300 (compared to standard HELIX-SFT specifications of >400 and >700) for the high and low mass spurs, respectively. The improvement allows for full resolution of hydrocarbons (C3+) at masses 37 - 40 and almost full resolution at mass 36. The HELIX-SFT will collect data in dual collection mode with 40Ar+ ion beams measured using the switchable 1011 - 1012 Ω resistor Faraday cup and 39Ar through 36Ar measured using the SEM. The HELIX-SFT requires Faraday-SEM inter-calibration but negates the necessity to inter-calibrate multiple electron multipliers. We will further present preliminary data from the dating of mineral standards: Alder Creek sanidine, Fish Canyon sanidine and Mount Dromedary biotite (GA1550).

Molecular dynamics simulations were used to investigate trends in noblegas (Ar, Kr, Xe) diffusion in the metal-organic frameworks HKUST-1 and ZIF-8. Diffusion occurs primarily through inter-cage jump events, with much greater diffusion of guest atoms in HKUST-1 compared to ZIF-8 due to the larger cage and window sizes in the former. We compare diffusion coefficients calculated for both rigid and flexible frameworks. For rigid framework simulations, in which the framework atoms were held at their crystallographic or geometry optimized coordinates, sometimes dramatic differences in guest diffusion were seen depending on the initial framework structure or the choice of frameworkmore » force field parameters. When framework flexibility effects were included, argon and krypton diffusion increased significantly compared to rigid-framework simulations using general force field parameters. Additionally, for argon and krypton in ZIF-8, guest diffusion increased with loading, demonstrating that guest-guest interactions between cages enhance inter-cage diffusion. No inter-cage jump events were seen for xenon atoms in ZIF-8 regardless of force field or initial structure, and the loading dependence of xenon diffusion in HKUST-1 is different for rigid and flexible frameworks. Diffusion of krypton and xenon in HKUST-1 depends on two competing effects: the steric effect that decreases diffusion as loading increases, and the “small cage effect” that increases diffusion as loading increases. Finally, a detailed analysis of the window size in ZIF-8 reveals that the window increases beyond its normal size to permit passage of a (nominally) larger krypton atom.« less

Molecular dynamics simulations were used to investigate trends in noblegas (Ar, Kr, Xe) diffusion in the metal-organic frameworks HKUST-1 and ZIF-8. Diffusion occurs primarily through inter-cage jump events, with much greater diffusion of guest atoms in HKUST-1 compared to ZIF-8 due to the larger cage and window sizes in the former. We compare diffusion coefficients calculated for both rigid and flexible frameworks. For rigid framework simulations, in which the framework atoms were held at their crystallographic or geometry optimized coordinates, sometimes dramatic differences in guest diffusion were seen depending on the initial framework structure or the choice of framework force field parameters. When framework flexibility effects were included, argon and krypton diffusion increased significantly compared to rigid-framework simulations using general force field parameters. Additionally, for argon and krypton in ZIF-8, guest diffusion increased with loading, demonstrating that guest-guest interactions between cages enhance inter-cage diffusion. No inter-cage jump events were seen for xenon atoms in ZIF-8 regardless of force field or initial structure, and the loading dependence of xenon diffusion in HKUST-1 is different for rigid and flexible frameworks. Diffusion of krypton and xenon in HKUST-1 depends on two competing effects: the steric effect that decreases diffusion as loading increases, and the “small cage effect” that increases diffusion as loading increases. Finally, a detailed analysis of the window size in ZIF-8 reveals that the window increases beyond its normal size to permit passage of a (nominally) larger krypton atom.

Gas holdup tests were performed in bench-scale and small-scale mechanically-agitated mixing systems at the Savannah River National Laboratory (SRNL) for a simulant of waste from the Hanford Tank 241-AZ-101. These featured additions of DOW Corning Q2-3183A anti-foam agent. Results indicated that this anti-foam agent (AFA) increased gas holdup in the waste simulant by about a factor of four and, counter-intuitively, that the holdup increased as the non-newtonian simulant shear strength decreased (apparent viscosity decreased). Such results raised the potential of increased flammable gas retention in Hanford Waste Treatment and Immobilization Plant (WTP) vessels mixed by air sparging and pulse-jet mixers (PJMs) during a Design Basis Event (DBE). Additional testing was performed to determine the effects of simulant properties, composition of alternate AFAs, and presence of trace noble metals. Key results are that: (1) Increased gas holdup resulting from addition of Q2-3183A is due to a decrease in surface tension that supports small bubbles which have low rise velocities. (2) Dow Corning 1520-US AFA shows it to be a viable replacement to Dow Corning Q2-3183A AFA. This alternative AFA, however, requires significantly higher dosage for the same anti-foam function. (3) Addition of noble metals to the AZ-101 waste simulant does not produce a catalytic gas retention effect with the AFA.

Recent advances in large cluster projectiles for secondary ion mass spectrometry (SIMS) allow the intact ions of some protein molecules to be detected without a matrix. However, detailed mechanisms of soft-sputtering and ionization of biomolecules remain unknown. Herein we investigate the secondary ion emission from insulin films under argon, krypton, and methane cluster ion bombardment. The intact insulin ion intensity significantly decreases for (CH4)1500+ ion bombardment compared with Ar1500+ ion bombardment at the same energy range of 3.3 eV/atom (or molecule), even though collisions with energetic methane clusters should generate numerous protons on the surface, which would enhance the ionization probability through proton attachment. In contrast, the intact ion intensity is almost the same for Ar2500+ and Kr2500+ cluster ion bombardment at the same energy range of 2 eV/atom. These observations suggest that detailed mechanisms for the ionization and sputtering by gas cluster ions should be investigated to enhance the intact ion intensity.

We report a theoretical analysis of electron-ion collision rates in xenon gas clusters irradiated by femtosecond laser pulses. The present analysis is based on the eikonal approximation (EA), the first Born approximation (FBA) and the classical (CL) methods. The calculations are performed using the plasma-screened Rogers potential introduced by Moll et al. [J. Phys. B. 43, 135103 (2010)] as well as the Debye potential for a wide range of experimental parameters. We find that the magnitudes of electron-ion collision frequency obtained in the EA do not fall as rapidly with the kinetic energy of electrons as in the FBA and CL methods for higher charge states of xenon ion (Xe8+ and Xe14+). Furthermore, EA shows that the effect of the inner structure of ion is most dominant for the lowest charge state of xenon ion (Xe1+). In the case of the present effective potential, FBA overestimates the CL results for all three different charge states of xenon, whereas for the Debye potential, both the FBA and CL methods predict collision frequencies which are nearly close to each other.

Zeolites are important industrial catalysts with porous three-dimensional structures. The catalytically active sites are located inside the pores, thus rendering them inaccessible for surface science measurements. We synthesized a two-dimensional (2D) zeolite model system, consisting of an (alumino)silicate bilayer weakly bound to a Ru (0001) surface. The 2D zeolite is suitable for surface science studies; it allows a detailed characterization of the atomic structure of the active site and interrogation of the model system during the catalytic reaction. As an initial step, we use Ar adsorption to obtain a better understanding of the atomic structure of the 2D zeolite. In addition, atomic level studies of rare gas adsorption and separation by zeolite are important for its potential application in nuclear waste sequestration. Experimental studies found that Ar atoms can be trapped inside the 2D-zeolite, raising an interesting question on whether Ar atoms are trapped inside the hexagonal prism nano-cages or at the interface between the (alumino)silicate bilayer and Ru(0001), or both. DFT calculations using van der Waals density functionals were carried out to determine the preferred Ar adsorption sites and the corresponding adsorption energies. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

A chamber for trapping soil gases as they evolve from the soil without disturbance to the soil and to the natural microclimate within the chamber has been invented. The chamber opens between measurements and therefore does not alter the metabolic processes that influence soil gas efflux rates. A multiple chamber system provides for repetitive multi-point sampling, undisturbed metabolic soil processes between sampling, and an essentially airtight sampling chamber operating at ambient pressure.

A mass spectrometer and computer system was developed for conducting a fundamental study on gasmonitoring in CELSS. Respiration and metabolism of the hamster and photosynthesis of the Spirulina were measured in a combination system consisting of a hamster chamber and a Spirulina cultivator. They are connected through a membrane gas exchanger. Some technical problems were examined. In the mass spectrometric gasmonitoring, a simultaneous multi-sample measurement was developed by employing a rotating exchange valve. Long term precise measurement was obtained by employing an automatic calibration system. The membrane gas sampling probe proved to be useful for long term measurement. The cultivation rate of the Spirulina was effectively changed by controlling CO2 and light supply. The experimental results are helpful for improving the hamster-spirulina system.

A mass spectrometer and computer system was developed for conducting a fundamental study on gasmonitoring in a Controlled Ecological Life Support System. Respiration and metabolism of the hamster and photosynthesis of the Spirulina were measured in a combination system consisting of a hamster chamber and a Spirulina cultivator. They are connected through a membrane gas exchanger. Some technical problems were examined. In the mass spectrometric gasmonitoring, a simultaneous multisample measurement was developed by employing a rotating exchange valve. Long term precise measurement was obtained by employing an automatic calibration system. The membrane gas sampling probe proved to be useful for long term measurement. The cultivation rate of the Spirulina was effectively changed by controlling CO2 and light supply. The experimental results are helpful for improving the hamster-spirulina system.

A novel class of interesting insertion compounds obtained through the insertion of a noblegas atom into the heavier pnictides have been explored by various ab initio quantum chemical techniques. Recently, the first neutral noblegas insertion compounds, FXeY (Y = P, N), were theoretically predicted to be stable; the triplet state was found to be the most stable state, with a high triplet-singlet energy gap, by our group. In this study, we investigated another noblegas inserted compound, FNgY (Ng = Kr and Xe; Y = As, Sb and Bi), with a triplet ground state. Density functional theory (DFT), second order Møller-Plesset perturbation theory (MP2), coupled-cluster theory (CCSD(T)) and multi-reference configuration interaction (MRCI) based techniques have been utilized to investigate the structures, stabilities, harmonic vibrational frequencies, charge distributions and topological properties of these compounds. These predicted species, FNgY (Ng = Kr and Xe; Y = As, Sb and Bi) are found to be energetically stable with respect to all the probable 2-body and 3-body dissociation pathways, except for the 2-body channel leading to the global minimum products (FY + Ng). Nevertheless, the finite barrier height corresponding to the saddle points of the compounds connected to their respective global minima products indicates that these compounds are kinetically stable. The structural parameters, energetics, and charge distribution results as well as atoms-in-molecules (AIM) analysis suggest that these predicted molecules can be best represented as F(-)[(3)NgY](+). Thus, all the aforementioned computed results clearly indicate that it may be possible to experimentally prepare the most stable triplet state of FNgY molecules under cryogenic conditions through a matrix isolation technique. PMID:27079448

It has been analyzed at the MP2/def2-QZVPPD level whether EX3+ (E = C-Pb; X = H, F-Br) can bind noblegas atoms. Geometrical and electronic structures, dissociation energy values, thermochemical parameters, natural bond order, electron density, and energy decomposition analyses highlight the possibility of such noblegas bound EX3+ compounds. Except He and Ne, the other heavier congeners of this family make quite strong bonds with E. In fact, the dissociations of Ar-Rn bound analogues turn out to be endergonic in nature at 298 K, except in the cases of ArGe Cl3+, Ar/KrGeBr3+, and ArSnBr3+. GeH3+ and EF3+ (E = Ge-Pb) can even bind two Ng atoms with reasonably high dissociation energy. As the pz orbital of the E center in EX3+ plays a crucial role in its binding with the noblegas atoms, the effect of the π back-bonding causing X → E electron transfer ought to be properly understood. Due to the larger back-donation, the Ng binding ability of EX3+ gradually decreases along F to Br. EH2+ and the global minimum HE(+…) H2 (E = Sn, Pb) complexes are also able to bind Ar-Rn atoms quite effectively. The NgE bonds in Ar-Rn bound CH3+, GeH3+, and EF3+ (E = Ge-Pb) and Xe/RnE bonds in NgECl3+ and NgEBr3+ (E = Ge, Sn) are mainly of covalent type. PMID:26132752

The electric dipole polarizabilities evaluated at imaginary frequencies for hydrogen, the alkali-metal atoms, the alkaline-earth atoms, and the noble gases are tabulated along with the resulting values of the atomic static polarizabilities, the atom-surface interaction constants, and the dispersion (or van der Waals) constants for the homonuclear and the heteronuclear diatomic combinations of the atoms.

Integral cross section experiments involving rotationally hot CH3OH projectiles and noblegas (Ng = Ne, Ar, Kr and Xe) targets are reported for the first time. Measured data have been exploited to characterize the phenomenological radial interaction in the CH3OH-Ng weakly bound complexes. Potential energy surfaces for all the systems have been formulated on the basis of a pairwise additive multicenter model. The comparison of model predictions with the most relevant experimental findings suggests that in CH3OH-Ng complexes, at variance with the behavior of the analogous complexes involving water or ammonia, the interaction is mainly due to van der Waals and induction components.

Noble gases are widely used as tracers to both determine fluid origin and identify transfer processes governing fluid flow in natural systems. This work presents the preliminary results and interpretations from submarine gas samples collected during the GAZCOGNE2 cruise (2013). The seepage activity and the spatial distribution of the widespread emission sites encountered at this area are described by (Dupré et al. 2014). Gas composition shows that methane is the dominant species compared to the C2+. The associated δ13C and δD signatures point to a biogenic origin- through CO2 reduction- of the gas. Helium concentrations are very low, ranging from 0.1 and 2.3 ppm, indicating a low residence time of the fluids in the subsurface. However, the resulting helium isotopic ratios are mostly crustal fingerprinted (around 0.02). The R/Ra values sometimes exhibit higher value of 0.2, indicative either an ASW (air saturated water) value, or the fingerprint of ancient mantle helium, the later in agreement with the geological structural context of the Parentis Basin. Most of the samples exhibit a mixing between ASW and air, probably by excess air addition to the initial ASW concentration. The elemental Ne/Ar ratio is remarkably constant for the totality of the samples, with a value typical of ASW (0.2). This result implies that the migrating gas phase is "stripping" the original water matrix from its noblegas content, as described by Gillfillian et al., 2008. This further indicates that an intermediate reservoir of biogenic gas should be present at depth. The GAZCOGNE study is co-funded by TOTAL and IFREMER as part of the PAMELA (Passive Margin Exploration Laboratories) scientific project. References: Dupré, S., L. Berger, N. Le Bouffant, C. Scalabrin, and J. F. Bourillet (2014), Fluid emissions at the Aquitaine Shelf (Bay of Biscay, France): a biogenic origin or the expression of hydrocarbon leakage?, Continental Shelf Research, doi:10.1016/j.csr.2014.07.004. Gilfillan S

Continuous intra-arterial blood gasmonitoring is a potentially valuable tool in the surgical and intensive care arenas. Patient oxygenation and acid base status can change rapidly and without warning. The ability to monitor pHa, PaCO2 and PaO2 in arterial blood will be a major medical advance for the anesthesiologist and intensivist. Intra-arterial blood gas sensors are typically placed in radial arteries. In certain patient populations accurate monitoring is not possible in radial arteries due to arterial environmental factors such as hypotension, vasoconstriction and atherosclerotic disease. These same factors can make radial cannulation difficult resulting in traumatic catheter insertion, thereby further compromising flow conditions. In situations where radial artery flow is expected to be compromised, selecting a large vessel for sensor placement is desirable. We report an initial feasibility study of our blood gasmonitoring system using the femoral artery as the sensing site. Clinical results are presented as well as potential advantages and disadvantages associated with monitoring in the femoral artery.

Residual CO2 saturation is a critically important parameter in CO2 storage as it can have a large impact on the available secure storage volume and post-injection CO2 migration. A suite of single-well tests to measure residual trapping was conducted at the Otway test site in Victoria, Australia during 2011. One or more of these tests could be conducted at a prospective CO2 storage site before large-scale injection. The test involved injection of 150 tonnes of pure carbon dioxide followed by 454 tonnes of CO2-saturated formation water to drive the carbon dioxide to residual saturation. This work presents a brief overview of the full test sequence, followed by the analysis and interpretation of the tests using noblegas tracers. Prior to CO2 injection krypton (Kr) and xenon (Xe) tracers were injected and back-produced to characterise the aquifer under single-phase conditions. After CO2 had been driven to residual the two tracers were injected and produced again. The noble gases act as non-partitioning aqueous-phase tracers in the undisturbed aquifer and as partitioning tracers in the presence of residual CO2. To estimate residual saturation from the tracer test data a one-dimensional radial model of the near-well region is used. In the model there are only two independent parameters: the apparent dispersivity of each tracer and the residual CO2 saturation. Independent analysis of the Kr and Xe tracer production curves gives the same estimate of residual saturation to within the accuracy of the method. Furthermore the residual from the noblegas tracer tests is consistent with other measurements in the sequence of tests.

We use noblegas concentrations and multiple isotopic tracers in groundwater and stream water in a small high elevation catchment to provide a snapshot of temperature, altitude, and physical processes at the time of recharge; and to determine subsurface residence times of different groundwater components. They identify three sources that contribute to groundwater flow: (1) seasonal groundwater recharge with short travel times, (2) water from bedrock aquifers that have elevated radiogenic {sup 4}He, and (3) upwelling of deep fluids that have 'mantle' helium and hydrothermal carbon isotope signatures. Although a bimodal distribution in apparent groundwater age indicates that groundwater storage times range from less than a year to several decades, water that recharges seasonally is the largest likely contributor to stream baseflow. Under climate change scnearios with earlier snowmelt, the groundwater that moves through the alluvial aquifer seasonally will be depleted earlier, providing less baseflow and possible extreme low flows in the creek during summer and fall. Dissolved noblegas measurements indciate recharge temperatures are 5 to 11 degrees higher than would be expected for direct influx of snowmelt, and that excess air concentrations are lower than would be expected for recharge through bedrock fractures. Instead, recharge likely occurs over diffuse vegetated areas, as indicated by {delta}{sup 13}C-DIC values that are consistent with incorporation of CO{sub 2} from soil respiration. Recharge temperatures are close to or slightly higher than mean annual air temperature, and are consistent with recharge during May and June, when snowpack melting occurs.

The paper presents the architectural design of flue gas continuous emission monitoring system, which uses computer, acquisition card and serial port communication card as hardware in the flue gas continuous emission monitoring system. In the CEMS, continuous emission monitoring system, it monitors dust in the flue gas, SO2, NOX, and some parameter on the flue gas emission, which includes mass flow, pressure, and temperature. For the software in the monitoring system, the research designs monitoring program in VC++, and realizes flue gasmonitor with the architecture.

Terrestrial planets and chondrites have noblegas platforms that are sufficiently alike, especially Ne/Ar, that they may have acquired their noble gases by similar processes. Meteorites presumably obtained their noble gases during formation in the solar nebula. Adsorption onto C - the major gas carrier in chondrites - is the likely mechanism for trapping noble gases; recent laboratory simulations support this hypothesis. The story is more complex for planets. An attractive possibility is that the planets acquired their noble gases in a late accreting veneer of chondritic material. In chondrites, noble gases correlate with C, N, H, and volatile metals; by Occam's Razor, we would expect a similar coupling in planets. Indeed, the Earth's crust and mantle contain chondritic like trace volatiles and PL group metals, respectively and the Earth's oceans resemble C chondrites in their enrichment of D (8X vs 8-10X of the galactic D/H ratio). Models have been proposed to explain some of the specific noblegas patterns in planets. These include: (1) noble gases may have been directly trapped by preplanetary material instead of arriving in a veneer; (2) for Venus, irradiation of preplanetary material, followed by diffusive loss of Ne, could explain the high concentration of AR-36; (3) the Earth and Venus may have initially had similar abundances of noble gases, but the Earth lost its share during the Moon forming event; (4) noble gases could have been captured by planetestimals, possibly leading to gravitational fractionation, particularly of Xe isotopes and (5) noble gases may have been dissolved in the hot outer portion of the Earth during contact with a primordial atmosphere.

Despite the abundance of SO2(g) in magmatic gases, precursory increases in magmatic SO2(g) are not always observed prior to volcanic eruption, probably because many terrestrial volcanoes contain abundant groundwater or surface water that scrubs magmatic gases until a dry pathway to the atmosphere is established. To better understand scrubbing and its implications for volcano monitoring, we model thermochemically the reaction of magmatic gases with water. First, we inject a 915??C magmatic gas from Merapi volcano into 25??C air-saturated water (ASW) over a wide range of gas/water mass ratios from 0.0002 to 100 and at a total pressure of 0.1 MPa. Then we model closed-system cooling of the magmatic gas, magmatic gas-ASW mixing at 5.0 MPa, runs with varied temperature and composition of the ASW, a case with a wide range of magmatic-gas compositions, and a reaction of a magmatic gas-ASW mixture with rock. The modeling predicts gas and water compositions, and, in one case, alteration assemblages for a wide range of scrubbing conditions; these results can be compared directly with samples from degassing volcanoes. The modeling suggests that CO2(g) is the main species to monitor when scrubbing exists; another candidate is H2S(g), but it can be affected by reactions with aqueous ferrous iron. In contrast, scrubbing by water will prevent significant SO2(g) and most HCl(g) emissions until dry pathways are established, except for moderate HCl(g) degassing from pH 100 t/d (tons per day) of SO2(g) in addition to CO2(g) and H2S(g) should be taken as a criterion of magma intrusion. Finally, the modeling suggests that the interpretation of gas-ratio data requires a case-by-case evaluation since ratio changes can often be produced by several mechanisms; nevertheless, several gas ratios may provide useful indices for monitoring the drying out of gas pathways. Published by Elsevier Science B.V.

The last decade has seen a dramatic increase in domestic energy production from unconventional reservoirs. This energy boom has generated marked economic benefits, but simultaneously evoked significant concerns regarding the potential for drinking-water contamination in shallow aquifers. Presently, efforts to evaluate the environmental impacts of shale gas development in the northern Appalachian Basin (NAB), located in the northeastern US, are limited by: (1) a lack of comprehensive "pre-drill" data for groundwater composition (water and gas); (2) uncertainty in the hydrogeological factors that control the occurrence of naturally present CH4 and brines in shallow Upper Devonian (UD) aquifers; and (3) limited geochemical techniques to quantify the sources and migration of crustal fluids (specifically methane) at various time scales. To address these questions, we analyzed the noblegas, dissolved ion, and hydrocarbon gas geochemistry of 72 drinking-water wells and one natural methane seep all located ≫1 km from shale gas drill sites in the NAB. In the present study, we consciously avoided groundwater wells from areas near active or recent drilling to ensure shale gas development would not bias the results. We also intentionally targeted areas with naturally occurring CH4 to characterize the geochemical signature and geological context of gas-phase hydrocarbons in shallow aquifers of the NAB. Our data display a positive relationship between elevated [CH4], [C2H6], [Cl], and [Ba] that co-occur with high [4He]. Although four groundwater samples show mantle contributions ranging from 1.2% to 11.6%, the majority of samples have [He] ranging from solubility levels (∼45 × 10-6 cm3 STP/L) with below-detectable [CH4] and minor amounts of tritiogenic 3He in low [Cl] and [Ba] waters, up to high [4He] = 0.4 cm3 STP/L with a purely crustal helium isotopic end-member (3He/4He = ∼0.02 times the atmospheric ratio (R/Ra)) in samples with CH4 near saturation for shallow

A silicon-based microhotplate tin oxide (SnO2) gas sensor integrated into a polymer-based microfluidic system for monitoring of contaminants in water systems is presented. This device is designed to sample a water source, control the sample vapor pressure within a microchannel using integrated resistive heaters, and direct the vapor past the integrated gas sensor for analysis. The sensor platform takes advantage of novel technology allowing direct integration of discrete silicon chips into a larger polymer microfluidic substrate, including seamless fluidic and electrical interconnects between the substrate and silicon chip.

Ambient seismic noise can be used to image spatial anomalies in the subsurface, without the need of recordings from seismic sources, such as earthquakes or explosions. Furthermore, the temporal variation of ambient seismic noise's can be used to infer temporal changes of the seismic velocities in the investigated medium. Such temporal variations can reflect changes of several physical properties/conditions in the medium. For example, they may be consequence of stress changes, variation of hydrogeological parameters, pore pressure and saturation changes due to fluid injection or extraction. Passive image interferometry allows to continuously monitor small temporal changes of seismic velocities in the subsurface, making it a suitable tool to monitor time-variant systems such as oil and gas reservoirs or volcanic environments. The technique does not require recordings from seismic sources in the classical sense, but is based on the processing of noise records. Moreover, it requires only data from one or two seismic stations, their locations constraining the sampled target area. Here we apply passive image interferometry to monitor a gas storage reservoir in northern Italy. The Collalto field (Northern Italy) is a depleted gas reservoir located at 1500 m depth, now used as a gas storage facility. The reservoir experience a significant temporal variation in the amount of stored gas: the injection phases mainly occur in the summer, while the extraction take place mostly in winter. In order to monitor induced seismicity related to gas storage operations, a seismic network (the Collalto Seismic Network) has been deployed in 2011. The Collalto Seismic Network is composed by 10 broadband stations, deployed within an area of about 20 km x 20 km, and provides high-quality continuous data since January 1st, 2012. In this work we present preliminary results from ambient noise interferometry using a two-months sample of continuous seismic data, i.e. from October 1st, 2012, to the

Chemical and isotope data were obtained for the active gas and noblegas of inclusion fluids in coarse-grained samples of magmatic-hydrothermal and magmatic-steam alunite from well-studied deposits (Marysvale, Utah; Tambo, Chile; Tapajo??s, Brazil; Cactus, California; Pierina, Peru), most of which are discussed in this Volume. Primary fluid inclusions in the alunite typically are less than 0.2 ??m but range up to several micrometers. Analyses of the active-gas composition of these alunite-hosted inclusion fluids released in vacuo by both crushing and heating indicate consistent differences in the compositions of magmatic-hydrothermal and magmatic-steam fluids. The compositions of fluids released by crushing were influenced by contributions from significant populations of secondary inclusions that trapped largely postdepositional hydrothermal fluids. Thermally released fluids gave the best representation of the fluids that formed primary alunite. The data are consistent with current models for the evolution of magmatic-hydrothermal and magmatic-steam fluids. Magmatic-steam fluids are vapor-dominant, average about 49 mol% H2O, and contain N2, H2, CH4, CO, Ar, He, HF, and HCl, with SO2 the dominant sulfur gas (average SO2/ H2S=202). In contrast, magmatic-hydrothermal fluids are liquid-dominant, average about 88 mol% H2O, and N2, H2, CO2, and HF, with H2S about as abundant as SO2 (average SO2/H2 S=0.7). The low SO2/H2S and N2/Ar ratios, and the near-absence of He in magmatic-hydrothermal fluids, are consistent with their derivation from degassed condensed magmatic fluids whose evolution from reduced-to-oxidized aqueous sulfur species was governed first by rock and then by fluid buffers. The high SO2/H2S and N2/Ar with significant concentrations of He in magmatic-steam fluids are consistent with derivation directly from a magma. None of the data supports the entrainment of atmospheric gases or mixing of air-saturated gases in meteoric water in either magmatic

Models of Earth's volatile acquisition and evolution attempt to reproduce the current noblegas abundances and isotopic composition of the mantle reservoirs. The volatile composition of the OIB reservoir - assumed to preserve a higher proportion of primordial noble gases than the degassed MORB reservoir - is a strong constraint for those models. However, the correct values of the neon and argon isotopic ratios in OIBs are still a subject of debate, because of the contamination of the samples by air-derived noble gases. Although there is no consensus on the origin of this contamination - is it empty vesicles or cracks in volcanic glasses filled with seawater; air dissolution in the magma at the timing of magma eruption; assimilation of oceanic crust in the magma chamber?- targeting directly with a laser the vesicle to analyse in volcanic glasses is an efficient way to reduce this contamination. Here we present analyses of individual vesicles of an Icelandic volcanic glass, DICE 11, that was extensively studied in the past by crushing pieces of the volcanic glass under vacuum, because it was considered to have a pure plume origin. The mm-sized sample was imaged tomographically with a 5μm resolution. For opening bubbles, we used a 193nm Excimer laser to avoid diffusion of noble gases by local heating. CO2 contents were estimated by pressure measurement in the laser cell using a sensitive manometer. We analysed He and Ar isotopes, plus 22Ne abundance on a Helix SFT mass-spectrometer. We also present new He, Ne and Ar compositions obtained by step crushing on similar samples (DICE 10 and DICE 11). 3He/4He isotopic ratios are homogeneous in all the vesicles and consistent with analyses by crushing, about 18Ra. Precise 40Ar/36Ar isotopic ratios were obtained on the largest vesicles only, due to high blank contribution to the smallest vesicles, and are about 9000, i.e. the highest values obtained by step-crushing. Considering that the Ar and He isotopic compositions

Gas having stable isotopes is monitored continuously by using a system that sends a modulated laser beam to the gas and collects and transmits the light not absorbed by the gas to a detector. Gas from geological storage, or from the atmosphere can be monitored continuously without collecting samples and transporting them to a lab.

In an ionization type detector for high energy radiation wherein the energy of incident radiation is absorbed through the ionization of a liquid noblegas and resulting free charge is collected to form a signal indicative of the energy of the incident radiation, an improvement comprising doping the liquid noblegas with photosensitive molecules to convert scintillation light due to recombination of ions, to additional free charge.

Quantum chemical calculations at the MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ levels have been carried out for the title compounds. The electronic structures were analyzed with a variety of charge and energy partitioning methods. All molecules possess linear equilibrium structures with D∞h symmetry. The total bond dissociation energies (BDEs) of the strongly bonded halogen anions [XHX](-) and [XAuX](-) decrease from [FHF](-) to [IHI](-) and from [FAuF](-) to [IAuI](-) . The BDEs of the noblegas compounds [NgHNg](+) and [NgAuNg](+) become larger for the heavier atoms. The central hydrogen and gold atoms carry partial positive charges in the cations and even in the anions, except for [IAuI](-) , in which case the gold atom has a small negative charge of -0.03 e. The molecular electrostatic potentials reveal that the regions of the most positive or negative charges may not agree with the partial charges of the atoms, because the spatial distribution of the electronic charge needs to be considered. The bonding analysis with the QTAIM method suggests a significant covalent character for the hydrogen bonds to the noblegas atoms in [NgHNg](+) and to the halogen atoms in [XHX](-) . The covalent character of the bonding in the gold systems [NgAuNg](+) and [XAuX](-) is smaller than in the hydrogen compound. The energy decomposition analysis suggests that the lighter hydrogen systems possess dative bonds X(-) →H(+) ←X(-) or Ng→H(+) ←Ng while the heavier homologues exhibit electron sharing through two-electron, three-center bonds. Dative bonds X(-) →Au(+) ←X(-) and Ng→Au(+) ←Ng are also diagnosed for the lighter gold systems, but the heavier compounds possess electron-shared bonds. PMID:27381200

Generally, the present disclosure is directed to gasmonitoring systems that use inductive power transfer to safely power an electrically passive device included within a nuclear material storage container. In particular, the electrically passive device can include an inductive power receiver for receiving inductive power transfer through a wall of the nuclear material storage container. The power received by the inductive power receiver can be used to power one or more sensors included in the device. Thus, the device is not required to include active power generation components such as, for example, a battery, that increase the risk of a spark igniting flammable gases within the container.

The Hazardous Gas Detection Lab (HGDL) at Kennedy Space Center is involved in the design and development of instrumentation that can detect and quantify various hazardous gases. Traditionally these systems are designed for leak detection of the cryogenic gases used for the propulsion of the Shuttle and other vehicles. Mass spectrometers are the basis of these systems, which provide excellent quantitation, sensitivity, selectivity, response times and detection limits. A Table lists common gases monitored for aerospace applications. The first five gases, hydrogen, helium, nitrogen, oxygen, and argon are historically the focus of the HGDL.

We measured the isotopic concentrations of long-lived and stable He, Ne, Ar, Kr, and Xe isotopes in a sample from a lead-bismuth eutectic target irradiated with 1.0 and 1.4 GeV protons. Our data indicate for most noble gases nearly complete release with retention fractions in the range of percent or less. Higher retention fractions result from the decay of long-lived radioactive progenitors from groups 1, 2, or 7 of the periodic table. From the data we can calculate a retention fraction for 3H of 2-3%. For alkaline metals we find retention fractions of about 10%, 30%, and 50% for Na, Rb, and Cs, respectively. For the alkaline earth metal Ba we found complete retention. Finally, the measured Kr and Xe concentrations indicate that there was some release of the halogens Br and I during and/or after the irradiation.

The COSC project (Collisional Orogeny in the Scandinavian Caledonides) drilled a 2496 m deep hole in Åre (Sweden) to deliver insights into mid-Palaeozoic mountain building processes from continent-continent collision, to improve our understanding of the hydrogeological-hydrochemical state and geothermal gradient of the mountain belt and to study the deep biosphere in the metamorphic rocks and crystalline basement. COSC was the first slimhole drilling project where online gasmonitoring of drilling mud was conducted during continuous wireline coring. Gas was continuously extracted at the surface from the circulating drilling mud with a gas-water separator, pumped in a nearby laboratory container and analysed in real-time with a quadrupole mass spectrometer for argon, methane, helium, carbon dioxide, nitrogen, oxygen, hydrogen, and krypton. Gas samples were taken from the gas line for laboratory studies on chemical composition of hydrocarbons, noblegas isotopes and stable isotopes. Every drill core created a gas peak identified in the drilling mud ~20-30 min after core arrival at the surface. With known core depth and surface arrival time, these gas peaks could be attributed to depth. As a result, nearly complete gas depth profiles at three meter intervals were obtained from 662 m (installation of the gas-water separator) to 2490 m depth. Maximum concentrations of non-atmospheric gasses in drilling mud were ~200 ppmv helium, ~300 ppmv methane and ~2 vol-% hydrogen. Helium peaks between ~900 m and 1000 m and correlates with enhanced concentrations of methane. Methane and hydrogen exhibit maximum concentrations below 1630 m depth where helium concentrations remain low. Integration of the drilling mud gasmonitoring dataset with data from geophysical downhole logging and core analysis is ongoing to help clarifying provenances and origin of gasses.

Despite the abundance of SO 2(g) in magmatic gases, precursory increases in magmatic SO 2(g) are not always observed prior to volcanic eruption, probably because many terrestrial volcanoes contain abundant groundwater or surface water that scrubs magmatic gases until a dry pathway to the atmosphere is established. To better understand scrubbing and its implications for volcano monitoring, we model thermochemically the reaction of magmatic gases with water. First, we inject a 915°C magmatic gas from Merapi volcano into 25°C air-saturated water (ASW) over a wide range of gas/water mass ratios from 0.0002 to 100 and at a total pressure of 0.1 MPa. Then we model closed-system cooling of the magmatic gas, magmatic gas-ASW mixing at 5.0 MPa, runs with varied temperature and composition of the ASW, a case with a wide range of magmatic-gas compositions, and a reaction of a magmatic gas-ASW mixture with rock. The modeling predicts gas and water compositions, and, in one case, alteration assemblages for a wide range of scrubbing conditions; these results can be compared directly with samples from degassing volcanoes. The modeling suggests that CO 2(g) is the main species to monitor when scrubbing exists; another candidate is H 2S (g), but it can be affected by reactions with aqueous ferrous iron. In contrast, scrubbing by water will prevent significant SO 2(g) and most HCl (g) emissions until dry pathways are established, except for moderate HCl (g) degassing from pH<0.5 hydrothermal waters. Furthermore, it appears that scrubbing will prevent much, if any, SO 2(g) degassing from long-resident boiling hydrothermal systems. Several processes can also decrease or increase H 2(g) emissions during scrubbing making H 2(g) a poor choice to detect changes in magma degassing. We applied the model results to interpret field observations and emission rate data from four eruptions: (1) Crater Peak on Mount Spurr (1992) where, except for a short post-eruptive period, scrubbing appears

We measured the concentrations and isotopic compositions of He, Ne, and Ar in bulk samples and metal separates of 14 ordinary chondrite falls with long exposure ages and high metamorphic grades. In addition, we measured concentrations of the cosmogenic radionuclides 10Be, 26Al, and 36Cl in metal separates and in the nonmagnetic fractions of the selected meteorites. Using cosmogenic 36Cl and 36Ar measured in the metal separates, we determined 36Cl-36Ar cosmic-ray exposure (CRE) ages, which are shielding-independent and therefore particularly reliable. Using the cosmogenic noble gases and radionuclides, we are able to decipher the CRE history for the studied objects. Based on the correlation 3He/21Ne versus 22Ne/21Ne, we demonstrate that, among the meteorites studied, only one suffered significant diffusive losses (about 35%). The data confirm that the linear correlation 3He/21Ne versus 22Ne/21Ne breaks down at high shielding. Using 36Cl-36Ar exposure ages and measured noblegas concentrations, we determine 21Ne and 38Ar production rates as a function of 22Ne/21Ne. The new data agree with recent model calculations for the relationship between 21Ne and 38Ar production rates and the 22Ne/21Ne ratio, which does not always provide unique shielding information. Based on the model calculations, we determine a new correlation line for 21Ne and 38Ar production rates as a function of the shielding indicator 22Ne/21Ne for H, L, and LL chondrites with preatmospheric radii less than about 65 cm. We also calculated the 10Be/21Ne and 26Al/21Ne production rate ratios for the investigated samples, which show good agreement with recent model calculations.

A gas sensor measures O.sub.2 content of a reformable monitoredgas containing hydrocarbons H.sub.2 O and/or CO.sub.2, preferably in association with an electrochemical power generation system. The gas sensor has a housing communicating with the monitoredgas environment and carries the monitoredgas through an integral catalytic hydrocarbon reforming chamber containing a reforming catalyst, and over a solid electrolyte electrochemical cell used for sensing purposes. The electrochemical cell includes a solid electrolyte between a sensor electrode that is exposed to the monitoredgas, and a reference electrode that is isolated in the housing from the monitoredgas and is exposed to a reference gas environment. A heating element is also provided in heat transfer communication with the gas sensor. A circuit that can include controls operable to adjust operations via valves or the like is connected between the sensor electrode and the reference electrode to process the electrical signal developed by the electrochemical cell. The electrical signal varies as a measure of the equilibrium oxygen partial pressure of the monitoredgas. Signal noise is effectively reduced by maintaining a constant temperature in the area of the electrochemical cell and providing a monitoredgas at chemical equilibria when contacting the electrochemical cell. The output gas from the electrochemical cell of the sensor is fed back into the conduits of the power generating system.

A gas sensor measures O{sub 2} content of a reformable monitoredgas containing hydrocarbons, H{sub 2}O and/or CO{sub 2}, preferably in association with an electrochemical power generation system. The gas sensor has a housing communicating with the monitoredgas environment and carries the monitoredgas through an integral catalytic hydrocarbon reforming chamber containing a reforming catalyst, and over a solid electrolyte electrochemical cell used for sensing purposes. The electrochemical cell includes a solid electrolyte between a sensor electrode that is exposed to the monitoredgas, and a reference electrode that is isolated in the housing from the monitoredgas and is exposed to a reference gas environment. A heating element is also provided in heat transfer communication with the gas sensor. A circuit that can include controls operable to adjust operations via valves or the like is connected between the sensor electrode and the reference electrode to process the electrical signal developed by the electrochemical cell. The electrical signal varies as a measure of the equilibrium oxygen partial pressure of the monitoredgas. Signal noise is effectively reduced by maintaining a constant temperature in the area of the electrochemical cell and providing a monitoredgas at chemical equilibria when contacting the electrochemical cell. The output gas from the electrochemical cell of the sensor is fed back into the conduits of the power generating system. 4 figs.

Current abundances of radiogenic noble gases (4-He, 40-Ar, 129-Xe) in the planetary atmospheres provide valuable information on planetary evolution through their degassing histories. Of these, 40-Ar (from 40-K with half life 1.25 Ga) can be used to envisage long-term degassing from their interior. Present amounts of 36 and 40-Ar should have information on timing and degree of degassing from the interior. On the other hand, 129-Xe (from 129-I with half life 17 Ma) is used in discussing early planetary degassing. Because life time of helium in the atmosphere is short, atmospheric 4-He (from 235-U, 238-U, 232-Th) data might be used only for current degassing. The relative abundance of 40-Ar in the Cytherean atmosphere is 0.26 of that in the Earth's atmosphere. We have executed numerical calculation of a 40-Ar degassing model along with mantle evolution and melt migration. Our result shows that the average magma production rate on Venus is about 5 (km(exp 3)/yr). Duration of plate motion on Venus, if existed, would be less than several hundred million years.

Portable spectrometer using photosensitive readouts, monitors the amount of oxygen and hydrogen in the inert gas shield of a tungsten-inert gas welding process. A fiber optic bundle transmits the light from the welding arc to the spectrometer.

The Hazardous Gas Detection Lab is involved in the design and development of instrumentation that can detect and quantify various hazardous gases. Traditionally these systems are designed for leak detection of the cryogenic gases used for the propulsion of the Shuttle and other vehicles. Mass spectrometers are the basis of these systems, which provide excellent quantitation, sensitivity, selectivity, response and limits of detection. Unfortunately, these systems are large, heavy and expensive. This feature limits the ability to perform gas analysis in certain applications. Smaller and lighter mass spectrometer systems could be used in many more applications primarily due to the portability of the system. Such applications would include air analysis in confined spaces, in-situ environmental analysis and emergency response. In general, system cost is lowered as size is reduced. With a low cost air analysis system, several systems could be utilized for monitoring large areas. These networked systems could be deployed at job-sites for worker safety, throughout a community for pollution warnings, or dispersed in a battlefield for early warning of chemical or biological threats. Presented will be information on the first prototype of this type of system. Included will be field trial data, with this prototype performing air analysis autonomously from an aircraft.

The electronic spectrum of the CUO molecule was investigated with the IHFSCC-SD (intermediate Hamiltonian Fock-space coupled cluster with singles and doubles) method and with TD-DFT (time-dependent density functional theory) employing the PBE and PBE0 exchange-correlation functionals. The importance of both spin-orbit coupling and correlation effects on the low-lying excited-states of this molecule are analyzed and discussed. Noblegas matrix effects on the energy ordering and vibrational frequencies of the lowest electronic states of the CUO molecule were investigated with density functional theory (DFT) and TD-DFT in a supermolecular as well as a frozen density embedding (FDE) subsystem approach. This data is used to test the suitability of the FDE approach to model the influence of different matrices on the vertical electronic transitions of this molecule. The most suitable potential was chosen to perform relativistic wave function theory in density functional theory calculations to study the vertical electronic spectra of the CUO and CUONg4 with the IHFSCC-SD method.

Information on the ocean/atmosphere state over the period spanning the Last Glacial Maximum - from the Late Pleistocene to the Holocene - provides crucial constraints on the relationship between orbital forcing and global climate change. The Pacific Ocean is particularly important in this respect because of its dominant role in exporting heat and moisture from the tropics to higher latitudes. Through targeting groundwaters in the Mojave Desert, California, we show that noblegas derived temperatures in California averaged 4.2 ?? 1.1 ??C cooler in the Late Pleistocene (from ???43 to ???12 ka) compared to the Holocene (from ???10 to ???5 ka). Furthermore, the older groundwaters contain higher concentrations of excess air (entrained air bubbles) and have elevated oxygen-18/oxygen-16 ratios (??18O) - indicators of vigorous aquifer recharge, and greater rainfall amounts and/or more intense precipitation events, respectively. Together, these paleoclimate indicators reveal that cooler and wetter conditions prevailed in the Mojave Desert from ???43 to ???12 ka. We suggest that during the Late Pleistocene, the Pacific ocean/atmosphere state was similar to present-day El Nino-like patterns, and was characterized by prolonged periods of weak trade winds, weak upwelling along the eastern Pacific margin, and increased precipitation in the southwestern U.S.

The effect of hydration on the fluorine free organo-noblegas compound HKrCCH and the role of krypton in the stabilization of the hydrated HKrCCH complexes have been investigated using the quantum chemical calculations on the HKrCCH-(H2O)n=1-6 clusters. Structure and energetics calculations show that water stabilizes HKrCCH through the π hydrogen bond in which the OH group of water interacts with the C[triple bond, length as m-dash]C group of HKrCCH. A maximum of four water molecules can directly interact with the C[triple bond, length as m-dash]C of HKrCCH and after that only inter-hydrogen bonding takes place between the water molecules indicating that the primary hydration shell contains four water molecules. Atom in molecule analysis depicts that π hydrogen bonded complexes of the hydrated HKrCCH are cyclic structures in which the OKr interaction cooperates in the formation of strong O-HC[triple bond, length as m-dash]C interaction. Structure, energetics and charge analysis clearly established that krypton plays an important role in the stabilization as well as the formation of the primary hydration shell of hydrated HKrCCH complexes. PMID:26523809

Background Following kidney transplantation, ischemia-reperfusion injury contributes to adverse outcomes. The purpose of this study was to determine whether a cold-storage solution saturated with noblegas (xenon or argon) could limit ischemia-reperfusion injury following cold ischemia. Methods Sixty Wistar rats were randomly allocated to 4 experimental groups. Kidneys were harvested and then stored for 6 h before transplantation in cold-storage solution (Celsior®) saturated with either air, nitrogen, xenon or argon. A syngenic orthotopic transplantation was performed. Renal function was determined on days 7 and 14 after transplantation. Transplanted kidneys were removed on day 14 for histological and immunohistochemical analyses. Results Creatinine clearance was significantly higher and urinary albumin significantly lower in the argon and xenon groups than in the other groups at days 7 and 14. These effects were considerably more pronounced for argon than for xenon. In addition, kidneys stored with argon, and to a lesser extent those stored with xenon, displayed preserved renal architecture as well as higher CD-10 and little active caspase-3 expression compared to other groups. Conclusion Argon- or xenon-satured cold-storage solution preserved renal architecture and function following transplantation by reducing ischemia-reperfusion injury. PMID:22470401

High resolution infrared absorption spectra for the upsilon/sub 3/ mode of SeF/sub 6/ in low temperature noblegas matrices have been observed. A remarkable amount of structure is observed leading to the conclusion that multiple trapping sites as well as site symmetry splittings, similar to those observed previously for SF/sub 6/, are common. Temperature dependent studies give a rich display of dynamics arising from host--guest interactions. These give evidence for dynamic exchange among equivalent low symmetry sites within a given trapping cage. This exchange is evidence for a dephasing of the components of upsilon/sub 3/ by a local site phonon mode in resonance with part of the phonon bath. Unexpected matrix shifts and intensity changes with temperature have been observed. Accurate isotope shifts, especially in a neon matrix, are shown to be useful for calculation of potential constants. A discussion of host--guest interactions, dephasing, and dynamic site exchange in these matrices is given.

The optimized-effective-potential (OEP) method and a method developed recently by Krieger, Li, and Iafrate (KLI) are applied to the band-structure calculations of noble-gas and alkali halide solids employing the self-interaction-corrected (SIC) local-spin-density (LSD) approximation for the exchange-correlation energy functional. The resulting band gaps from both calculations are found to be in fair agreement with the experimental values. The discrepancies are typically within a few percent with results that are nearly the same as those of previously published orbital-dependent multipotential SIC calculations, whereas the LSD results underestimate the band gaps by as much as 40%. As in the LSD---and it is believed to be the case even for the exact Kohn-Sham potential---both the OEP and KLI predict valence-band widths which are narrower than those of experiment. In all cases, the KLI method yields essentially the same results as the OEP.

We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H2/Ar and 2 using H2/He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration. Graphical Abstract ᅟ. PMID:27380389

Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd(+) in the gas phase. While a lysozyme-Au adduct forms Au18(+), Au25(+), Au38(+) and Au102(+) ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag(+), Pt(2+), Pd(2+), Cu(2+), Fe(2+), Ni(2+) and Cr(3+)) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38(+). While other metal ions like Cu(2+) help forming Au25(+) selectively, Fe(2+) catalyzes the formation of Au25(+) over all other clusters. Gas phase cluster formation occurs from protein adducts where Au is in the 1+ state while Pd is in the 2+ state. The creation of alloys in the gas phase is not affected whether a physical mixture of Au and Pd adducts or a Au and Pd co-adduct is used as the precursor. The formation of Au cores and AuPd alloy cores of the kind comparable to monolayer protected clusters implies that naked clusters themselves may be nucleated in solution. PMID:24146135

We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H2/Ar and 2 using H2/He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration.

We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H2/Ar and 2 using H2/He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration.

Unlike other lakes in the McMurdo Dry Valleys, Antarctica, Lake Vida has a thick (~ 19 m) ice cover sealing a liquid brine body of unusually high salinity (~ 245 g/L) from the atmosphere. To constrain the conditions under which the atypical Lake Vida ice cover formed and evolved, 19 ice samples were collected down to a depth of ~ 14 m, together with three brine samples trapped in the ice at ~ 16 m for analysis of helium, neon, argon, krypton, and xenon concentrations. The broad pattern of noblegas concentrations for Lake Vida samples is fundamentally different from that of air saturated water (ASW) at 0 °C and an elevation of 340 m for salinities of 0 (ice) and 245 g/L (brine). Overall, ice samples are enriched in He and depleted in Ne with saturation relative to ASW averages of 1.38 and 0.82, respectively, and strongly depleted in Ar, Kr, and Xe with relative saturations of 0.10, 0.06, and 0.05, respectively. By contrast, brine samples are generally depleted in He and Ne (relative saturation averages of 0.33 and 0.27, respectively) but enriched in Ar, Kr, and Xe, with relative saturation averages of 1.45, 3.15, and 8.86, respectively. A three-phase freezing partitioning model generating brine, ice and bubble concentrations for all stable noble gases was tested and compared with our data. Measured brine values are best reproduced for a salinity value of 175 g/L, a pressure of 1.1 atm, and a bubble volume of 20 cm 3 kg -1. Sensitivity tests for ice + bubble samples show an ideal fit for bubble volumes of ~ 1-2 cm 3 kg -1. Our results show that the conditions under which ice and brine formed and evolved at Lake Vida are significantly different from other ice-covered lakes in the area. Our brine data suggest that Lake Vida may be transitioning from a wet to a dry-based lake, while the ice + bubble data suggest at least partial re-equilibration of residual liquid with the atmosphere as ice forms at the top of Lake Vida ice cover.

To characterize the heavy noblegas composition of MORBs we present new He, Ne, Ar, and Xe abundances and isotopic compositions from the equatorial Mid-Atlantic Ridge. Both depleted MORBs nominally devoid of plume influence and more enriched MORBs thought to represent the influence of a HIMU mantle plume are present in close geographical proximity in this region. Ne-Ar-Xe isotopic compositions in individual step-crushes are correlated, which, along with significant radiogenic excesses, allows correction for shallow-level air contamination. Based on the relationship between the noble gases and the lithophile isotopes (Sr, Nd and Pb), the depleted MORB mantle has a 21Ne/22Ne between 0.0617 and 0.0646, 40Ar/36Ar ratio of 41,500±9000 and 129Xe/130Xe ratio of 7.77±0.06. On the other hand, the HIMU-type MORBs are characterized by far less radiogenic Ne, Ar and Xe isotopic compositions with mantle source 21Ne/22Ne between 0.0544 and 0.0610, and 40Ar/36Ar and 129Xe/130Xe ratios of 18,100±600 and 7.21±0.06, respectively. The observation of less nucleogenic 21Ne/22Ne in HIMU-type MORBs is similar to observations from HIMU ocean islands and requires the HIMU plume to be comprised of both recycled and primitive material. Within the depleted MORBs we observe He and Ne to be negatively correlated. The observation suggests that along the equatorial Atlantic the most depleted MORBs are related to normal MORBs through the addition of a small proportion of a HIMU plume component. Our new Xe isotopic measurements demonstrate distinct 129Xe/136Xe ratios in the mantle sources of depleted MORBs, HIMU-type MORBs and the Iceland plume. While substantial injection of atmospheric Xe into these mantle sources is implied, the differences in Xe isotopic composition cannot result solely from recycling of air. Rather, they require that mantle plumes sample a reservoir less degassed than the depleted MORB mantle. This conclusion is consistent with a higher proportion of Pu- to U

The gas push-pull test (GPPT) is a single-well gas-tracer method to quantify in situ rates of CH4 oxidation in soils. To improve the design and interpretation of GPPT field experiments, gas component transport during GPPTs was examined in abiotic porous media over a range of water saturations (0.0 < or = Sw < or = 0.61). A series of GPPTs using He, Ne, and Ar as tracers for CH4 were performed at two injection/extraction gas flow rates (approximately 200 and approximately 700 mL min(-1)) in a laboratory tank. Extraction phase breakthrough curves and mass recovery curves of the gaseous components became more similar at higher Sw as water in the pore space restricted diffusive gas-phase transport. Diffusional fractionation of the stable carbon isotopes of CH4 during the extraction period of GPPTs also decreased with increasing Sw (particularly when Sw > 0.42). Gas-component transport during GPPTs was numerically simulated using estimated hydraulic parameters for the porous media and no fitting of data for the GPPTs. Numerical simulations accurately predicted the relative decline of the gaseous components in the breakthrough curves, but slightly overestimated recoveries at low Sw (< or = 0.35) and underestimated recoveries at high Sw (> or = 0.49). Comparison of numerical simulations considering and not considering air-water partitioning indicated that removal of gaseous components through dissolution in pore water was not significant during GPPTs, even at Sw = 0.61. These data indicate that Ar is a good tracer for CH4 physical transport over the full range of Sw studied, whereas, at Sw > 0.61, any of the tracers could be used. Greater mass recovery at higher Sw raises the possibility to reduce gas flow rates, thereby extending GPPT times in environments such as tundra soils where low activity due to low temperatures may require longer test times to establish a quantifiable difference between reactant and tracer breakthrough curves. PMID:18504990

Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd+ in the gas phase. While a lysozyme-Au adduct forms Au18+, Au25+, Au38+ and Au102+ ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag+, Pt2+, Pd2+, Cu2+, Fe2+, Ni2+ and Cr3+) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38+. While other metal ions like Cu2+ help forming Au25+ selectively, Fe2+ catalyzes the formation of Au25+ over all other clusters. Gas phase cluster formation occurs from protein adducts where Au is in the 1+ state while Pd is in the 2+ state. The creation of alloys in the gas phase is not affected whether a physical mixture of Au and Pd adducts or a Au and Pd co-adduct is used as the precursor. The formation of Au cores and AuPd alloy cores of the kind comparable to monolayer protected clusters implies that naked clusters themselves may be nucleated in solution.Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd+ in the gas phase. While a lysozyme-Au adduct forms Au18+, Au25+, Au38+ and Au102+ ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag+, Pt2+, Pd2+, Cu2+, Fe2+, Ni2+ and Cr3+) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38+. While other metal ions like Cu2+ help forming Au25+ selectively, Fe2+ catalyzes the formation of Au25+ over all other clusters. Gas phase cluster

The Raman enhancing ability of noble metal nanoparticles (NPs) is an important factor for surface enhanced Raman scattering (SERS) substrate screening, which is generally evaluated by simply mixing as-prepared NPs with Raman reporters for Raman signal measurements. This method usually leads to incredible results because of the NP surface coverage nonuniformity and reporter-induced NP aggregation. Moreover, it cannot realize in situ, continuous SERS characterization. Herein, we proposed a dynamic SERS monitoring strategy for NPs with precisely tuned structures based on a simplified spatially confined NP growth method. Gold nanorod (AuNR) seed NPs were coated with a mesoporous silica (mSiO2) shell. The permeability of mSiO2 for both reactive species and Raman reporters rendered the silver overcoating reaction and SERS indication of NP growth. Additionally, the mSiO2 coating ensured monodisperse NP growth in a Raman reporter-rich reaction system. Moreover, "elastic" features of mSiO2 were observed for the first time, which is crucial for holding the growing NP without breakage. This feature makes the mSiO2 coating adhere to metal NPs throughout the growing process, providing a stable Raman reporter distribution microenvironment near the NPs and ensuring that the substrate's SERS ability comparison is accurate. Three types of NPs, i.e., core-shell Au@AgNR@mSiO2, Au@AuNR@mSiO2, and yolk-shell Au@void@AuNR@mSiO2 NPs, were synthesized via core-shell overgrowth and galvanic replacement methods, showing the versatility of the approach. The living cell SERS labeling ability of Au@AgNR@mSiO2-based tags was also demonstrated. This strategy addresses the problems of multiple batch NP preparation, aggregation, and surface adsorption differentiation, which is a breakthrough for the dynamic comparison of SERS ability of metal NPs with precisely tuned structures and optical properties. PMID:25815901

Colorimetric fiber optic sensors have been developed for measuring the pH and pCO2 of blood. These sensors are fabricated using a single 125 micrometers diameter optical fiber. Located at the distal end of the fiber is a capsule that contains a pH sensitive dye. The pCO2 sensor is fabricated from a pH sensor with the addition of a salt, bicarbonate, and the encapsulation with an ion impermeable gas permeable membrane. The distal end of the capsule is terminated with a reflective surface. The reflective surface can either be a polished metallic surface or, in this case, a TiO2 impregnated epoxy. The disposable sensor mates with an optical connector that contains two optical fibers of the same size as the disposable sensor. The two fibers within the optical cable provide a light path for both the antegrade and retrograde optical signals. These fibers are terminated at either the LED source or the detector. A prototype sensor assembly that incorporates the measurement of three physiological parameters (pH, pCO2, and sO2) has been demonstrated to fit within a standard 20 gauge arterial catheter, typically used for radial artery blood pressure monitoring, without significant damping of the blood pressure waveform. The pH sensor has a range of 6.9 - 7.8 with a precision of 0.01 pH units and the pCO2 sensor has a range of 15 - 95 mm Hg with a precision of 3 mm Hg. The long term drift pH drift is less than 0.01 pH unit per 8 hours and the pCO2 drift is less than 1 mm Hg per 8 hours. Sensor performance in the canine has demonstrated that the pH sensor is accurate to within +/- 0.03 pH units and the pCO2 sensor is accurate to within +/- 3 mm Hg when compared to a typical blood gas analyzer.

Rh/ceria catalysts were synthesized by flame spray pyrolysis for high temperature water gas shift (WGS) reactions. These catalysts show a high specific surface area due to a high degree of nanocrystallinity. X-ray absorption spectroscopy (XAS) unraveled the formation of small Rh particles under WGS reaction conditions. The catalytic activity was examined at atmospheric pressure by measuring CO conversion as a function of temperature. Some methane formation was observed above 310°C.

The essence of the positive-column plasma constriction for static (the diffusion mode) and dynamic ionization equilibrium (the stratificated and constricted modes) is analyzed. Two physical parameters, namely, the effective ionization rate of gas atoms and the ambipolar diffusion coefficient of electrons and ions, determine the transverse distribution of discharge species and affect the current states of plasma. Transverse constriction of the positive column takes place as the gas ionization level (discharge current) and pressure increase. The stratified mode (including the constricted one) is observed between the two adjacent types of self-sustained discharge phases when they coexist together at the same time or in the same place as a coherent binary mixture. In the case, a occurrence of the discharge phase with more high electron density presently involve a great decrease in the cross-section of the current channel for d.c. discharges. Additional physical factors, such as cataphoresis and electrophoresis phenomena and spatial gas density inhomogeneity correlated with a circulatory flow in d.c. discharges, are mainly responsible for the current hysteresis and partially constricted discharge.

This paper describes the operations of several types of gasmonitors in use at the Idaho National Laboratory (INL) High Temperature Electrolysis Experiment (HTE) laboratory. The gases monitored at hydrogen, carbon monoxide, carbon dioxide, and oxygen. The operating time, calibration, and unwanted alarms are described. The calibration session time durations are described. Some simple statistics are given for the reliability of these monitors and the results are compared to operating experiences of other types of monitors.

This paper describes pertinent design practices of selecting types of monitors, monitor unit placement, setpoint selection, and maintenance considerations for gasmonitors. While hydrogen gasmonitors and enriched oxygen atmosphere monitors as they would be needed for hydrogen production experiments are the primary focus of this paper, monitors for carbon monoxide and carbon dioxide are also discussed. The experiences of designing, installing, and calibrating gasmonitors for a laboratory where experiments in support of the DOE Nuclear Hydrogen Initiative (NHI) are described along with codes, standards, and regulations for these monitors. Information from the literature about best operating practices is also presented. The NHI program has two types of activities. The first, near-term activity is laboratory and pilot-plant experimentation with different processes in the kilogram per day scale to select the most promising types of processes for future applications of hydrogen production. Prudent design calls for indoor gasmonitors to sense any hydrogen leaks within these laboratory rooms. The second, longer-term activity is the prototype, or large-scale plants to produce tons of hydrogen per day. These large, outdoor production plants will require area (or “fencepost”) monitoring of hydrogen gas leaks. Some processes will have oxygen production with hydrogen production, and any oxygen releases are also safety concerns since oxygen gas is the strongest oxidizer. Monitoring of these gases is important for personnel safety of both indoor and outdoor experiments. There is some guidance available about proper placement of monitors. The fixed point, stationary monitor can only function if the intruding gas contacts the monitor. Therefore, monitor placement is vital to proper monitoring of the room or area. Factors in sensor location selection include: indoor or outdoor site, the location and nature of potential vapor/gas sources, chemical and physical data of the

Proper corrosion monitoring of gas gathering pipelines requires a system review to determine the appropriate monitor locations and types of monitoring techniques. This paper develops and discusses a classification of conditions such as flow regime and gas composition. Also discussed are junction categories which, for corrosion monitoring, need to be considered from two points of view. The first is related to fluid flow in the line and the second is related corrosion inhibitor movement along the pipeline. The appropriate application of the various monitoring techniques such as coupons, hydrogen detectors, electrical resistance probe and linear polarization probes are discussed in relation to flow regime and gas composition. Problems caused by semi-conduction from iron sulfide are considered. Advantages and disadvantages of fluid gathering methods such as pots and flow-through drips are discussed in relation to their reliability as on-line monitoring locations.

Global climate warming has become the focus question of international global climate change research, and is an important factor influencing world economy, political situation, and ecological environment. Produced carbon emission gases such as CO2, CH4, N2O, etc. caused by human activity are the main reason for global warming. In order to forecast future climate change and construct accurate carbon cycle model, monitoring accuracy of gas concentration from carbon emission must be improved. In the present paper, the newest progress in the international research results about monitoringgas concentration from carbon emissions by remote sensing was considered, monitoring method for carbon emissions was introduced, and remotely sensed monitoring technology about gas concentration from carbon emissions (including thermal infrared, sun spectrum, active remote sensing monitoring technology) was stated. In detail, several present and future satellite sensors were introduced (including TOVS, AIRS, IASI, SCIAMACHY, GOSAT, OCO, A-SCOPE and ASCENDS), and monitoring results achieved by these sensors were analyzed. PMID:22870656

Suggests two methods of developing the study of the noble gases: first, the discovery of the elements and recent discovery of xenon show the human face of chemistry (historical development); second, the properties of noblegas compounds (particularly xenon) can be used to test the framework of conventional chemistry. (Author/JM)

An apparatus and method are disclosed for separation of heavy noblegas in a gas volume. An apparatus and method have been devised which includes a reservoir containing an oil exhibiting a clathrate effect for heavy noble gases with a reservoir input port and the reservoir is designed to enable the input gas volume to bubble through the oil with the heavy noblegas being absorbed by the oil exhibiting a clathrate effect. The gas having reduced amounts of heavy noblegas is output from the oil reservoir, and the oil having absorbed heavy noblegas can be treated by mechanical agitation and/or heating to desorb the heavy noblegas for analysis and/or containment and allow recycling of the oil to the reservoir. 6 figs.

An apparatus and method for separation of heavy noblegas in a gas volume. An apparatus and method have been devised which includes a reservoir containing an oil exhibiting a clathrate effect for heavy noble gases with a reservoir input port and the reservoir is designed to enable the input gas volume to bubble through the oil with the heavy noblegas being absorbed by the oil exhibiting a clathrate effect. The gas having reduced amounts of heavy noblegas is output from the oil reservoir, and the oil having absorbed heavy noblegas can be treated by mechanical agitation and/or heating to desorb the heavy noblegas for analysis and/or containment and allow recycling of the oil to the reservoir.

The locations and roles of noble gases at an oxide/metal interface in oxide dispersed metal are theoretically and experimentally investigated. Oxide dispersed metal consisting of FCC Fe and Y2Hf2O7 (Y2Ti2O7) is synthesized by mechanical alloying under a saturated Ar gas environment. Transmission electron microscopy and density functional theory observes the strain field at the interface of FCC Fe {111} and Y2Hf2O7 {111} whose physical origin emerges from surface reconstruction due to charge transfer. Noble gases are experimentally observed at the oxide (Y2Ti2O7) site and calculations reveal that the noble gases segregate the interface and grow toward the oxide site. In general, the interface is defined as the trapping site for noble gases; however, transmission electron microscopy and density functional theory found evidence which shows that noble gases grow toward the oxide, contrary to the generally held idea that the interface is the final trapping site for noble gases. Furthermore, calculations show that the inclusion of He/Ar hardens the oxide, suggesting that material fractures could begin from the noblegas bubble within the oxides. Thus, experimental and theoretical results demonstrate that noble gases grow from the interface toward the oxide and that oxides behave as a trapping site for noble gases. PMID:26840881

An ideal-gas, quasi-steady, duct-flow model previously formulated for small scale gas-transfer problems is extended to real gases via the van der Waals equation of state as well as general virial expansions. The model is applicable for an arbitrary series of ducting components where each is described empirically by total pressure and total temperature change correlations. The adequacy of the van der Waals model for gas-transfer calculations is verified by comparisons with: (1) real gas PVT data; (2) the magnitudes of the controlling effects; and (3) approximate limiting case solutions with numerical results using more accurate real-gas modeling. 25 figures.

In this paper it was demonstrated empirically that disinfection with ozone can be controlled by monitoring the exhaust gas ozone concentration exiting the contactor. This method is more reliable than measuring dissolved ozone because of the inherent difficulties and inadequacies ...

Elizabeth Gas Co., a gas distribution company in New Jersey, has added a network of combustible gas sensors to a computer system already in place for continuous monitoring of gas leaks. The computer center at the company's Erie St. facility controls all dispatching, which includes routing gas through the system and controlling gas pressure. The system uses redundant Hewlett-Packard A900 central processing units (CPU), 6 monitors, including a Mitsubishi 35-in. color monitor, and Fisher control software. The company's primary tank farm, which contains over a million gallons of propane and LNG, is located near several chemical plants, an oil refinery and a residential neighborhood. To monitor for combustible leaks at the site, the company installed 49 stand-alone combustible gas sensors manufactured by Mine Safety Appliances Co. (MSA) of Pittsburgh, Pa. The sensors are designed to measure the concentrations of propane and LNG and trigger alarms at 20% of the lower explosive limit (LEL). The sensors are diffusion types that sample ambient air rather than drawing in samples through a pump. Using the principle of catalytic oxidation, the sensors produce a signal proportional to the concentration of combustible gas in the atmosphere. If gas is detected above 20% of the LEL, a relay driver signal is sent into a remote annunciator panel which contains LED alarm displays for each sensor. The remote annunciator panel also houses a 24 VDC power supply.

Relative production efficiencies of Mg and Al Auger electrons by He, Ne, Ar, Kr, and Xe ion bombardment are reported as a function of ion energy for energies not exceeding 3 keV. The experimental apparatus employed consisted of a LEED-Auger system equipped with an ion gun and a four-grid retarding-potential analyzer. It is found that: (1) the shape of the ion-excited Auger signal was independent of the rare gas and quite symmetric; (2) the Al signal was about an order of magnitude smaller than the Mg signal for a given bombarding species and ion-gun voltage; (3) no signal was observed for He(+) bombardment under any of the experimental conditions; (4) signal strengths were independent of temperature and ion dose; (5) the Auger production efficiencies differed by no more than a factor of two among the different gases - except for He(+) - on a given metal; (6) all the signal strengths increased with increasing ion-gun voltage, with no maximum exhibited; and (7) the apparent threshold energy for the Al signal was higher than that for the Mg signal. The differences between the results for the two metals are attributed to the fact that the Al 2p orbital lies deeper in energy and closer to the nucleus than the corresponding Mg orbital.

A method for indirect gas species monitoring based on measurements of selected gas species is disclosed. In situ absorption measurements of combustion species are used for process control and optimization. The gas species accessible by near or mid-IR techniques are limited to species that absorb in this spectral region. The absorption strength is selected to be strong enough for the required sensitivity and is selected to be isolated from neighboring absorption transitions. By coupling the gas measurement with a software sensor gas, species not accessible from the near or mid-IR absorption measurement can be predicted.

This paper summarizes the results of monitoring tank headspace for flammable gas release events. In over 40 tank years of monitoring the largest detected release in a single-shell tank is 2.4 cubic meters of Hydrogen. In the double-shell tanks the largest release is 19.3 cubic meters except in SY-101 pre mixer pump installation condition.

This document describes the verification monitoring campaign used to document the ability of the new ventilation system to mitigate flammable gas accumulation under steady state tank conditions. This document reports the results of the monitoring campaign. The ventilation system configuration, process data, and data analysis are presented.

It is shown that the main problem, arising when designing a stationary Raman gas analyzer intended to monitor gaseous air pollutions, is to get SRS signals of sufficient intensity. The engineering solutions are presented that provide the required sensitivity (~ 50-100 ppb). It is achieved by compressing a gas medium under analysis and gaining intensity of the exciting laser radiation.

Tanks 103-SY; 101-AW; 103-, 104-, and 105-AN are on the Flammable Gas Watch List. Recently, standard hydrogen monitoring system (SHMS) cabinets have been installed in the vent header of each of these tanks. Grab samples have been taken once per week, and a gas chromatograph was installed on tank 104-AN as a field test. The data that have been collected since gasmonitoring began on these tanks are summarized in this document.

Two monitoring proportional counters (MPCs), installed at the inlet and outlet of the gas system of BESIII drift chamber (DC), were used to monitor the operation of the BESIII DC successfully and effectively as reported in this paper. The ratio of Gout/Gin (full energy photoelectron peak position of 55Fe 5.9 keV X-ray in inlet MPC as Gin and outlet MPC as Gout) is used as the main monitoring parameter. The MPC method is very useful for the gas detector system.

There has been a recent revival of interest in the measurement of angular correlation of annihilation photons from the decay of positrons and positronium in gases. This revival has been stimulated by the possibility offered by the technique to shed new light on the apparently low positronium formation fraction in the heavier noble gases and to provide information on positronium quenching processes in gases such as oxygen. There is also the potential for learning about positronium slowing down in gases. This review focuses on experimental noblegas work and considers what new information has been, and may be, gained from these studies.

Apparatus employing ultrasonic energy for detecting and measuring the quantity of gas bubbles present in liquids being transported through pipes. An ultrasonic transducer is positioned along the longitudinal axis of a fluid duct, oriented to transmit acoustic energy radially of the duct around the circumference of the enclosure walls. The back-reflected energy is received centrally of the duct and interpreted as a measure of gas entrainment. One specific embodiment employs a conical reflector to direct the transmitted acoustic energy radially of the duct and redirect the reflected energy back to the transducer for reception. A modified embodiment employs a cylindrical ultrasonic transducer for this purpose.

Food is frequently packed in a controlled environment of gas, in order to extend shelf life. It is of great importance to be able to monitor the status of the packed food to ensure quality. We demonstrate a technique to monitor the gas inside packages non-intrusively by using a laser spectroscopic method in scattering solid materials. The technique named GASMAS (GAs in Scattering Media Absorption Spectroscopy) is based on tunable diode laser absorption spectroscopy and relies on the fact that free gas inside solid materials absorbs much sharper spectrally than the bulk material. Results from time dependent measurements of molecular oxygen and water vapour in packages of minced meat, bake-off bread, and the headspace of a milk carton are presented. We show that the technique allows gas measurements inside the food through the package, and assessment of the integrity of the package.

Mud gas logging has been commonly used in oil industry and continental scientific drilling to detect mainly hydrocarbon gases from the reservoir formation. Quick analysis of the gas provides almost real-time information which is critical to evaluate the formation and, in particular, safety of drilling operation. Furthermore, mud gasmonitoring complements the lack of core or fluid samples particularly in a deep hole, and strengthen interpretations of geophysical logs. In scientific ocean drilling, on the other hand, mud gasmonitoring was unavailable in riserless drilling through the history of DSDP and ODP, until riser drilling was first carried out in 2009 by D/V Chikyu. In IODP Exp 319, GFZ installed the same system with that used in continental drilling aboard Chikyu. High methane concentrations are clearly correlated with increased wood content in the cuttings. The system installation was, however, temporary and gas separator was moved during the expedition for a technical reason. In 2011, new mud gasmonitoring system was installed aboard Chikyu and was used for the first time in Exp 337. The gas separator was placed on a newly branched bypass mud flow line, and the gas sample was sent to analysis unit equipped with methane carbon isotope analyzer in addition to mass spectrometer and gas chromatograph. The data from the analytical instruments is converted to depth profiles by calculating the lag effects due to mud circulation. Exp 337 was carried out from July 26 to Sep 30, 2011, at offshore Shimokita peninsula, northeast Japan, targeting deep sub-seafloor biosphere in and around coal bed. Data from the hole C0020A, which was drilled to 2466 mbsf with riser drilling, provided insights into bio-geochemical process through the depth of the hole. In this presentation, we show the design of Chikyu's new mud gasmonitoring system, with preliminary data from Exp 337.

This article describes the operations of several types of gasmonitors in use at the Idaho National Laboratory (INL) High Temperature Electrolysis Experiment (HTE) laboratory. The gases monitored in the lab room are hydrogen, carbon monoxide, carbon dioxide, and oxygen. The operating time, calibration, and both actual and unwanted alarms are described. The calibration session time durations are described. In addition, some simple calculations are given to estimate the reliability of these monitors and the results are compared to operating experiences of other types of monitors.

An overview of the history and current status of research on planetary noble gases is presented. The discovery that neon and argon are vastly more abundant on Venus than on earth points to the solar wind rather than condensation as the fundamental process for placing noble gases in the atmospheres of the terrestrial planets; however, solar wind implantation may not be able to fully reproduce the observed gradient, nor does it obviously account for similar planetary Ne/Ar ratios and dissimilar planetary Ar/Kr ratios. More recent studies have emphasized escape rather than accretion. Hydrodynamic escape, which is fractionating, readily accounts for the difference between atmospheric neon and isotopically light mantle neon. Atmospheric cratering, which is nearly nonfractionating, can account for the extreme scarcity of nonradiogenic noble gases (and other volatiles) on Mars.

Noble metals used for dental castings continue to consist of alloys of gold, palladium, and silver (not a noble metal), with smaller amounts of iridium, ruthenium, and platinum. The majority are used as a backing for ceramic baking, with the rest used as inlays, onlays, and unveneered crowns. Base metal alloys, principally made of nickel, chromium, and beryllium have gained widespread usage, especially in the United States, due to their lower cost and higher mechanical properties. The current literature, for the most part, cites the use of noble alloys as controls for trials of alternative materials. Direct gold (gold foil) still retains a following and a number of new patents were founded. PMID:1777669

The authors' company has developed a machinery health monitoring system (MHealth) for short-term and long-term historical trending and analysis of data from its 40 gas compressor stations. The author discusses the benefits of real-time trending in troubleshooting operations, in preventative maintenance scheduling and cites specific applications in the startup operations of several new gas compressor/centrifugal compressor units.

Mass spectrometer fractionation bias (mass discrimination) is a ubiquitous phenomenon in noblegas mass spectroscopy and must be corrected for in order to obtain accurate-high precision isotopic ratios that are used in isotopic age calculations. Temporal variations in mass fractionation are well known phenomena and have been reported in several studies (eg. Turrin et al., 2010 and references therein). Here we report on the pressure dependency on mass spectrometer fractionation bias. In our experiment, we varied by a factor of five the signal size of aliquots of atmospheric argon delivered from an automated air pipette system. The measured mass discrimination difference (MD) as determined by the 40Ar/36Ar ratio between the 1-fold and 5-fold air pipette shots is ~5%. The air 40Ar/36Ar aliquots were measured using a MAP 215-50 operating in pulse counting mode. The air measurements were interspersed with measurements of Alder Creek (AC) sanidine and Fish Canyon (FC) sanidine that were co-irradiated for 0.75 hours. The grain sizes for the two mineral standards were chosen such that the AC sample yielded 40Ar signals of about 50 kcps, similar to that delivered by a single aliquot delivered by the air pipette. The FC grains were about 5-10 times greater (150-600 kcps) than the single air aliquot. Following the analyses, we applied the MD correction to both the FC and AC analyses. When the MD as determined from the single pipette data (which matches 40Ar beam intensity of the AC sample) is applied to both the AC and FC data a "J" of 1.579±0.001x10-4 is obtained from the FC data and an age of 1183 ±4 ka for AC. However, when the MD as determined from the multiple aliquot pipette data (with an 40Ar beam similar to that of the FC analyses) is applied to the FC data a "J" of 1.588±0.001x10-4 is obtained and an AC age of 1189 ±4 ka the same age at the 95% confidence level, the reported age for AC. We conclude that variation in MD over signal sizes typically analyzed in 40Ar

This software package interfaces with various gas stream devices such as pressure transducers, flow meters, flow controllers, valves, and analyzers such as a mass spectrometer. The software provides excellent user interfacing with various windows that provide time-domain graphs, valve state buttons, priority- colored messages, and warning icons. The user can configure the software to save as much or as little data as needed to a comma-delimited file. The software also includes an intuitive scripting language for automated processing. The configuration allows for the assignment of measured values or calibration so that raw signals can be viewed as usable pressures, flows, or concentrations in real time. The software is based on those used in two safety systems for shuttle processing and one volcanic gas analysis system. Mass analyzers typically have very unique applications and vary from job to job. As such, software available on the market is usually inadequate or targeted on a specific application (such as EPA methods). The goal was to develop powerful software that could be used with prototype systems. The key problem was to generalize the software to be easily and quickly reconfigurable. At Kennedy Space Center (KSC), the prior art consists of two primary methods. The first method was to utilize Lab- VIEW and a commercial data acquisition system. This method required rewriting code for each different application and only provided raw data. To obtain data in engineering units, manual calculations were required. The second method was to utilize one of the embedded computer systems developed for another system. This second method had the benefit of providing data in engineering units, but was limited in the number of control parameters.

This paper presents the recent development in engine gas-path components health monitoring using electrostatic sensors in combination with signal-processing techniques. Two ground-based engine electrostatic monitoring experiments are reported and the exhaust gas electrostatic monitoring signal-based fault-detection method is proposed. It is found that the water washing, oil leakage and combustor linear cracking result in an increase in the activity level of the electrostatic monitoring signal, which can be detected by the electrostatic monitoring system. For on-line health monitoring of the gas-path components, a baseline model-based fault-detection method is proposed and the multivariate state estimation technique is used to establish the baseline model for the electrostatic monitoring signal. The method is applied to a data set from a turbo-shaft engine electrostatic monitoring experiment. The results of the case study show that the system with the developed method is capable of detecting the gas-path component fault in an on-line fashion.

Traces the history of the "noble savage" concept, from the romantic view of the fifteenth through eighteenth centuries of American Indians as holdovers from the "golden age," to current media images of the medicine man or the Indian princess. Discusses how this patronizing stereotype continues to undermine Indian identity. (SV)

The development of an instrument for continuously monitoring SO2 levels in flue gas is proposed. The SO2 will be detected by means of an electrochemical sensor cell, which operates in a three-electrode potentiostatic mode. The proposed innovation is develop-ment of an advan...

Noblegas permeabilities and diffusivities of Kapton, butyl, nylon, and "Silver Shield" are measured at temperatures between 22 and 115C. The breakthrough times and solubilities at 22C are also determined. The relationship of the room temperature permeabilities to the noblegas atomic radii is used to estimate radon permeability for each material studied. For the noble gases tested, Kapton and Silver Shield have the lowest permeabilities and diffusivities, followed by nylon and butyl, respectively.

A solid state gas density monitor has been developed for SF/sub 6/ service in gas-insulated substation equipment that is based on principles and construction techniques similar to ionization-type fire alarms. The monitor has a resolution of .7kPa (.1 psi) at 20/sup 0/C and, depending on ion chamber voltage and geometry, exhibits a linearity of /sup +//sub -/1 to /sup +//sub -/4. kPa (/sup +//sub -/.15 to /sup +//sub -/.6 psi) at 20/sup 0/C over the density range 0.20 to 0.66 MPa (30 to 95 psia) at 20/sup 0/C. The monitor incorporates two level contact closure actuated by gas density falling below one of two pre-set alarm limits, and an LCD read-out for visual monitoring and instrument calibration. The display presents density in terms of equivalent psia at 68/sup 0/F. (20/sup 0/C.).

The noblegas (Ar, Kr, Xe) and halogen (Cl, Br, I) composition of fluid inclusions in hydrothermal quartz and calcite related to the hypogene iron oxide-copper-gold (IOCG) mineralization at Mantoverde and Candelaria, Chile, have been investigated to provide new insights of fluid and salinity sources in Andean IOCG deposits. A combination of mechanical extraction by crushing and thermal decrepitation methods was applied and collectively indicate that fluid inclusions with salinities ranging from 3.4 up to 64 wt% NaCl equivalent have molar Br/Cl and I/Cl ratios of between 0.5 × 10-3 and 3.0 × 10-3 and I/Cl of between 8 × 10-6 and 25 × 10-6 in the majority of samples, with maximum values of 5.2 × 10-3 obtained for Br/Cl and 64 × 10-6 for I/Cl in fluid inclusions within individual samples. The fluid inclusions have age-corrected 40Ar/36Ar ratios ranging from the atmospheric value of 296 up to 490 ± 45, indicating the presence of crustal- or mantle-derived excess 40Ar in the fluid inclusions of most samples. The fluid inclusions have 84Kr/36Ar and 130Xe/36Ar ratios intermediate of air and air-saturated water. However, 40Ar/36Ar is not correlated with either 84Kr/36Ar or 130Xe/36Ar, and the fluid inclusion 36Ar concentrations of 0.2-3.5 × 10-10 mol/g (calculated from measured Cl/36Ar and thermometric salinity measurements) extend below the seawater value of 0.34 × 10-10 mol/g, suggesting that contamination with modern air is a minor artifact. The range of fluid inclusion Br/Cl and I/Cl ratios overlap those previously documented for the mantle and magmatic-hydrothermal ore deposits, and the fluids' unusually low 36Ar concentration is consistent with the involvement of magmatic-hydrothermal fluids. Input of additional non-magmatic fluid components is suggested by the spread in Br/Cl and I/Cl to values characteristic of bittern brine sedimentary formation waters and near atmospheric 40Ar/36Ar. These data are compatible with mixing of magmatic-hydrothermal fluids

The cost of monitoring greenhouse gas emissions from landfill sites is of major concern for regulatory authorities. The current monitoring procedure is recognised as labour intensive, requiring agency inspectors to physically travel to perimeter borehole wells in rough terrain and manually measure gas concentration levels with expensive hand-held instrumentation. In this article we present a cost-effective and efficient system for remotely monitoring landfill subsurface migration of methane and carbon dioxide concentration levels. Based purely on an autonomous sensing architecture, the proposed sensing platform was capable of performing complex analytical measurements in situ and successfully communicating the data remotely to a cloud database. A web tool was developed to present the sensed data to relevant stakeholders. We report our experiences in deploying such an approach in the field over a period of approximately 16 months. PMID:22163975

The cost of monitoring greenhouse gas emissions from landfill sites is of major concern for regulatory authorities. The current monitoring procedure is recognised as labour intensive, requiring agency inspectors to physically travel to perimeter borehole wells in rough terrain and manually measure gas concentration levels with expensive hand-held instrumentation. In this article we present a cost-effective and efficient system for remotely monitoring landfill subsurface migration of methane and carbon dioxide concentration levels. Based purely on an autonomous sensing architecture, the proposed sensing platform was capable of performing complex analytical measurements in situ and successfully communicating the data remotely to a cloud database. A web tool was developed to present the sensed data to relevant stakeholders. We report our experiences in deploying such an approach in the field over a period of approximately 16 months. PMID:22163975

Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NO(x), and unburned hydrocarbons-need to be fully converted to CO(2), N(2), and H(2)O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al(2)O(3) or SiO(2) promoted by CeO(2). However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce(1-x)M(x)O(2-delta) and Ce(1-x-y)Ti(y)M(x)O(2-delta) (M = Pt, Pd, Rh; x = 0.01-0.02, delta approximately x, y = 0.15-0.25) oxides in fluorite structure. In these oxide catalysts, Pt(2+), Pd(2+), or Rh(3+) ions are substituted only to the extent of 1-2% of Ce(4+) ion. Lower-valent noble metal ion substitution in CeO(2) creates oxygen vacancies. Reducing molecules (CO, H(2), NH(3)) are adsorbed onto electron-deficient noble metal ions, while oxidizing (O(2), NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NO(x) reduction (with >80% N(2) selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO(2) or Ce(1-x)Ti(x)O(2) were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the

We investigate the thermal conductivity of suspended graphene nanoribbons in noble gaseous environments using molecular dynamics simulations. It is reported that the thermal conductivity of perfect graphene nanoribbons decreases with the gaseous pressure. The decreasing is more obvious for the noblegas with large atomic number. However, the gaseous pressure cannot change the thermal conductivity of defective graphene nanoribbons apparently. The phonon spectra of graphene nanoribbons are also provided to give corresponding supports.

Isotopic concentrations of noble gases were assessed in grain size separates of 14 soils from a 67-cm section of lunar regolith taken on the rim of Shorty Crater. The orange-black droplets in this section were probably formed from pyroclastic eruptions about 3.6 billion years ago; they give little indication of surface exposure. The isotopic concentrations suggest that cosmic ray irradiation of the core occurred in two stages and that the core stratigraphy was inverted between stages. The first irradiation stage may have taken place immediately after pyroclastic deposition of the droplets and could have lasted about 20 million years.

The continuous enrichment monitor, developed and fielded in the 1990s by the International Atomic Energy Agency, provided a go-no-go capability to distinguish between UF{sub 6} containing low enriched (approximately 4% {sup 235}U) and highly enriched (above 20% {sup 235}U) uranium. This instrument used the 22-keV line from a {sup 109}Cd source as a transmission source to achieve a high sensitivity to the UF{sub 6} gas absorption. The 1.27-yr half-life required that the source be periodically replaced and the instrument recalibrated. The instrument's functionality and accuracy were limited by the fact that measured gas density and gas pressure were treated as confidential facility information. The modern safeguarding of a gas centrifuge enrichment plant producing low-enriched UF{sub 6} product aims toward a more quantitative flow and enrichment monitoring concept that sets new standards for accuracy stability, and confidence. An instrument must be accurate enough to detect the diversion of a significant quantity of material, have virtually zero false alarms, and protect the operator's proprietary process information. We discuss a new concept for advanced gas enrichment assay measurement technology. This design concept eliminates the need for the periodic replacement of a radioactive source as well as the need for maintenance by experts. Some initial experimental results will be presented.

Over the past decade, detectors based on liquid noble elements have been at the frontier in the search for WIMP dark matter. They have been shown to powerfully combine low threshold, low background, recoil ID, large mass and self shielding, leading to unprecedented sensitivity to WIMP-nuclear recoil scatters. I will review the current suite of technologies and results to date, and provide an outlook for the coming years.

Noble metal additives significantly improve the performance of SnO2 based sensors. Recently, it has been found that X-ray absorption spectroscopy is an excellent tool to identify their structure under sensing conditions, despite of the low concentrations and the rather thin (50 μm) and highly porous layers. For this purpose a new in situ approach has been established and here we highlight the potential with an overview on the results of Pd-, Pt-, and Au-additives in SnO2-based sensors at work. Emphasis was laid on recording the structure (by XANES and EXAFS) and performance at the same time. In contrast to earlier studies, Pd- and Pt-additives were observed to be in oxidized and finely dispersed state under sensing conditions excluding a spillover from metallic noble metal particles. However, Au was mainly present as metallic particles in the sensing SnO2-layer. For the Pt- and Au-doped SnO2-layers high energy-resolved fluorescence detected X-ray absorption spectra (HERFD-XAS) were recorded not only to minimize the lifetime-broadening but also to eliminate the Au- and Pt-fluorescence effectively and to record range-extended EXAFS.

A battery operated electronic gas density monitor was developed for SF6 service in gas insulated substation equipment that is based on principles similar to ionization type fire alarms. The monitor has a resolution of 0.1 psia at 68 F and exhibits a linearity of from + or - 0.15 to + or - 0.6 psia at 68 F over the pressure range 30 to 75 psia, depending on ion chamber characteristics and operating voltage. A prototype unit exhibited a deviation from ideality of about 0.01% per degree Fahrenheit over the temperature range -30 F to 105 F and was found insensitive to water vapor in SF6 at levels in excess of 1000 ppM.

Chemical inertness, surface volatility and low abundance have made the noble gases a unique trace elemental and isotopic system for constraining the formation and evolution of the solid Earth and its atmosphere. This geochemical role parallels extensive physical-property measurements on the condensed rare gases alone at the pressures equivalent to those of the Earth's deep mantle and core from diamond-anvil cell (DAC) experiments. Traditional geochemical approaches to the processes of planetary evolution have involved crystal-melt partitioning at low pressures relevant more to near-surface degassing. The degree of compatibility has fluctuated among different studies and largely rests with the conclusion that, for common upper mantle phases, the noble gases are highly incompatible. But the long-known high 3He/4He ratios for some ocean-island basalts and more recent observations for some of the rare gases (Ne, Ar and possibly Xe) that there is a solar component emanating from the Earth, continue to raise questions on the source reservoir as well as on accretionary and incorporation processes. Changes in models of mantle convection style have made it harder to rely on the deep mantle as a reservoir, and the core has remained a particularly unfavourable location either because of difficulty in constructing a retention mechanism during planetary accretion or simply because of lack of data: Partitioning studies at pressure are rare and complicated by the difficulty in reproducing not only absolute concentrations, but confinement of gas in high-pressure apparatus and post-run analysis. We have investigated noblegas solubility in silicate liquids at high pressures in a DAC (relevant to a magma-ocean model of the early Earth) that suggests that the detailed composition and structure of silicate liquids may act as an important control on the level of incompatibility. The long-held idea of partial melting as a single-stage, efficient process for extracting noble gases from

A residual gas fluorescence beam profile monitor at the Relativistic Heavy Ion Collider (RHIC) has successfully recorded beam images of various species of relativistic heavy ions during FY2012 operations. These fully striped ions include gold, copper, and uranium at 100, 99.9, and 96.4GeV/n, respectively. Their beam profiles give an independent measurement of the RHIC beam size and emittance. We estimated their corresponding fluorescence cross sections to be 2.1×10-16, 1.8×10-17, and 2.6×10-16cm2, and obtained their rms transverse beam sizes of 0.36, 0.37, 0.24 mm for gold, copper, and uranium ions, respectively. They are the smallest ion beam width, thus lowest beam emittance, ever produced at RHIC or any other high-energy heavy ion colliders. These extremely small beam sizes may have reached a fundamental limit to residual gas fluorescence based beam profile monitor. Nevertheless, this beam diagnostic technique, utilizing the beam-induced fluorescence from residual gas where hydrogen is still the dominant constituent in nearly all vacuum systems, represents a passive, robust, truly noninvasive, monitor for high-energy ion beams.

The sequestration of CO2 in sub-seabed geological formations is one of the Carbon Capture and Storage (CCS) strategies currently under study. Although offshore operations are significantly more expensive than comparable onshore operations, the growing public resistance against onshore CCS projects makes sub-seabed storage a promising option. Even after a thorough review of the geological setting, there is always the possibility of leakage from the reservoir. As part of the EU-financed project CO2ReMoVe (Research, Monitoring, Verification), which aims to develop innovative research and technologies for monitoring and verification of carbon dioxide geological storage, we are working on the development of submarine long-term gas flow monitoring systems. The basic design of the monitoring system builds on our experience in volcano monitoring. Early prototypes were composed of a raft floating on the surface of a mud volcano, carrying sensors for CO2 flux and concentration, data storage and transmission, and power supply by battery-buffered solar panels. The system was modified for installation in open sea by using a buoy instead of a raft and a funnel on the seafloor to collect the gas, connected by a flexible tube. This setup provides a cost-effective solution for shallow waters. However, a buoy interferes with ship traffic, and it is also difficult to adapt this design to greater water depths. These requirements can best be complied by a completely submersed system. A system for unattended long-term monitoring in a marine environment has to be extremely durable. Therefore, we focussed on developing a mechanically and electrically as simple setup as possible, which has the additional advantage of low cost. The system consists of a funnel-shaped gas collector, a sensor head and pressure housings for electronics and power supply. Since this setup is inexpensive, it can be deployed in numbers to cover larger areas. By addition of multi-channel data loggers, data

One of the Carbon Capture and Storage (CCS) strategies currently under study is the sequestration of CO2 in sub-seabed geological formations. Even after a thorough review of the geological setting, there is the possibility of leaks from the reservoirs. As part of the EU-financed project CO2ReMoVe (Research, Monitoring, Verification), which aims to develop innovative research and technologies for monitoring and verification of carbon dioxide geological storage, we are working on the development of submarine long-term gas flow monitoring systems. Technically, however, these systems are not limited to CO2 but can be used for monitoring of any free gas emission (bubbles) on the seafloor. The basic design of the gas flow sensor system was derived from former prototypes developed for monitoring CO2 and CH4 on mud volcanoes in Azerbaijan. This design was composed of a raft floating on the surface above the gas vent to collect the bubbles. Sensors for CO2 flux and concentration and electronics for data storage and transmission were mounted on the raft, together with battery-buffered solar panels for power supply. The system was modified for installation in open sea by using a buoy instead of a raft and a funnel on the seafloor to collect the gas, which is then guided above water level through a flexible tube. Besides some technical problems (condensed water in the tube, movement of the buoys due to waves leading to biased measurement of flow rates), this setup provides a cost-effective solution for shallow waters. However, a buoy interferes with ship traffic, and it is also difficult to adapt this design to greater water depths. These requirements can best be complied by a completely submersed system. To allow unattended long-term monitoring in a submarine environment, such a system has to be extremely durable. Therefore, we focussed on developing a mechanically and electrically as simple setup as possible, which has the additional advantage of low cost. The system

Temporary gas storage facilities play a fundamental role in the design of energy supply. The evaluation and recognition of induced seismicity, geodetic displacements and wellbores damages are their main associated risks that should be minimized for a safe management of these facilities, especially in densely populated areas. Injection and withdrawal of gas into/from a porous reservoir generally lead reservoir rocks to deform. Rock deformation is due to variations of the state of stress of rocks, both in the reservoir and the surrounding: subsidence, wellbore damages and induced or activated seismicity are primary consequences of these variations. In this paper we present a case study on induced deformation by an exploited gas reservoir, converted to temporary natural gas storage since 1994, in North-Eastern Italy. The reservoir, composed by 2 independent carbonatic sandstone intervals, approximately 10 meters thick, and 1400 meters deep, has been exploited since 1983, recording a pressure drop of about 16 MPa. The inversion of gas pressure and volume data, together with a 26 year ground displacement dataset monitoring, allow us to define reservoir deformations, modelled by a semi-analytical method based on an equivalent Eshelby's inclusion problem, able to account for mechanical differences between reservoir and surrounding rocks. Stress field changes, and displacement fields around the reservoir and on the ground mainly represent the results of this modelling. A Coulomb Failure Stress analysis, performed by FEA, was applied to define and evaluate the influence of magnitude and shape of stress field changes on rock stability, highlighting rock volumes that mainly suffer stress changes eventually leading to induced/activated earthquakes. The microseismic monitoring provides then the control on failures and their location. The methodology here used provide a solid base for induced or activated seismicity risk assessment: it provides an easy tool to quantify magnitude

A device for detecting impurities in a noblegas includes a detection chamber and a source of pulsed ultraviolet light. The pulse of the ultraviolet light is transferred into the detection chamber and onto a photocathode, thereby emitting a cloud of free electrons into the noblegas within the detection chamber. The cloud of electrons is attracted to the opposite end of the detection chamber by a high positive voltage potential at that end and focused onto a sensing anode. If there are impurities in the noblegas, some or all of the electrons within the cloud will bond with the impurity molecules and not reach the sensing anode. Therefore, measuring a lower signal at the sensing anode indicates a higher level of impurities while sensing a higher signal indicates fewer impurities. Impurities in the range of one part per billion can be measured by this device.

Chemical and isotopic studies including analyses of noble gases were comprehensively conducted on the groundwater of the entire Kii Peninsula, which is located in the fore-arc region of southwest Japan. Groundwater of Na-Cl-HCO3, Na-HCO3-Cl, and Na-Cl types was shown to be distributed across the whole area. Groundwater in the inland central part of the peninsula shows relatively low salinity, whereas groundwater from the area along the ENE-trending Median Tectonic Line (MTL), on the north side of the peninsula, shows high salinity (up to 18,800 mg/L of Cl-) and the presence of unusual heavy oxygen isotopes. This trend is similar to that documented in saline waters from the Arima region (the so-called "Arima-type thermal water"). High 3He/4He ratios relative to the atmospheric value (up to 6.7 Ra) were recorded throughout the Kii Peninsula, covering a wider area than documented previously. The saline groundwater is also strongly depleted in 20Ne and heavy noble gases. From the wide distribution of high 3He/4He values and the associated 20Ne and Cl- concentrations, we infer that aqueous fluids derived from dehydration of the subducting slab are present at depth beneath almost the entire Kii Peninsula. These aqueous fluids may ascend along the major north-dipping boundary faults. The isotopic composition of groundwater from the southern part of the peninsula suggests that the contribution from these dehydration-derived fluids is relatively small in this region. However, volatile components (e.g., noble gases and CO2) in the groundwater of this area may originate from the dehydration-derived fluids. Upwelling of Arima-type thermal water of the Na-Cl-HCO3 type is expected to undergo a phase separation of volatile species due to decompression as the fluid ascends. The variety of water types documented may be due to this water-gas separation and the subsequent incorporation of gaseous species into shallow meteoric groundwater. The observed high 3He/4He ratios in the

Monitoring results for the first quarter of 1981 are listed. These include data from air surveillance, noblegas and tritium, milk surveillance, and TLD dosimetry networks and the available data from the long-term hydrological monitoring network. The only unusual radioactivity de...

Effective reservoir management is a Holy Grail of the oil and gas industry. Quest for new technologies is never ending but most often they increase effectiveness and decrease the costs. None of the newcomers proved to be a silver bullet in such a key metric of the industry as average oil recovery factor. This factor is still around 30 %, meaning that 70 % of hydrocarbon reserves are left in the ground in places where we already have expensive infrastructure (platforms, wells) to extract them. Main reason for this inefficiency is our inability to address realistic reservoir complexity. Most of the time we fail to properly characterize our reservoirs before production. As a matter of fact, one of the most important parameters -- permeability -- can not be mapped from remote geophysical methods. Therefore we always start production blind even though reservoir state before production is the simplest one. Once first oil is produced, we greatly complicate the things and quickly become unable to estimate the state and condition of the reservoir (fluid, pressures, faults etc) or oilfield hardware (wells, platforms, pumps) to make a sound next decision in the chain of reservoir management. Our modeling capabilities are such that if we know true state of the things - we can make incredibly accurate predictions and make extremely efficient decisions. Thus the bottleneck is our inability to properly describe the state of the reservoirs in real time. Industry is starting to recognize active monitoring as an answer to this critical issue. We will highlight industry strides in active geophysical monitoring from well to reservoir scale. It is worth noting that when one says ``monitoring" production technologists think of measuring pressures at the wellhead or at the pump, reservoir engineers think of measuring extracted volumes and pressures, while geophysicist may think of change in elastic properties. We prefer to think of monitoring as to measuring those parameters of the

Four ionization profile monitors (IPMs) in RHIC measure vertical and horizontal beam profiles in the two rings by measuring the distribution of electrons produced by beam ionization of residual gas. During the last three years both the collection accuracy and signal/noise ratio have been improved. An electron source is mounted across the beam pipe from the collector to monitor microchannel plate (MCP) aging and the signal electrons are gated to reduce MCP aging and to allow charge replenishment between single-turn measurements. Software changes permit simultaneous measurements of any number of individual bunches in the ring. This has been used to measure emittance growth rates on six bunches of varying intensities in a single store. Also the software supports FFT analysis of turn-by-turn profiles of a single bunch at injection to detect dipole and quadrupole oscillations.

The timing was right in the “evolution” of low power tunable diode laser spectroscopy (TDLS) to design a spacecraft cabin air monitor around technology being developed at a small company funded by SBIR grants. NASA Centers had been monitoring their progress hoping that certain key gaps in the long term gasmonitoring development roadmap could be filled by TDLS. The first iteration of a monitor for multiple gases called the Multi-GasMonitor (MGM) which measures oxygen, carbon dioxide, ammonia and water vapor, as well as temperature and pressure. In January 2013, the ISS Program being particularly interested in ammonia funded a technology demonstration of MGM. The project was a joint effort between Vista Photonics for the sensor, NASA-JSC for project management and laboratory calibration, and Nanoracks for the enclosure and payload certification/integration. Nanoracks was selected in order to use their new experimental infrastructure located in an EXPRESS rack in the JEM. The MGM enclosure has multiple power supply options including 5VDC USB interface to the Nanoracks Frame, 28VDC Express Rack power and internal rechargeable batteries. MGM was calibrated at NASA-JSC in July 2013, delivered to ISS on 37 Soyuz in November 2013 and was installed and activated in February 2014. MGM resided in the Nanoracks Frame making continuous measurements the majority of the time, but also spent a day in Node 3 on battery power, and a month in the US Lab Module on 28VDC power, as part of the demonstration. Data was downloaded via Nanoracks on roughly a weekly basis. Comparisons were made with data from the Major Constituents Analyzer (MCA) which draws and analyzes air from JEM and other modules several times per hour. A crewmember challenged the carbon dioxide channel by breathing into the intake upon startup, and challenged the ammonia channel later using a commercial ammonia inhalant. Many interesting phenomena in the cabin atmosphere were detected during the tech demo

Four ionization profile monitors (IPMs) are in RHIC to measure vertical and horizontal beam profiles in the two rings. These work by measuring the distribution of electrons produced by beam ionization of residual gas. During the last two years both the collection accuracy and signal/noise ratio have been improved. An electron source is mounted across the beam pipe from the collector to monitor microchannel plate (MCP) aging and the signal electrons are gated to reduce MCP aging and to allow charge replenishment between single-turn measurements. Software changes permit simultaneous measurements of any number of individual bunches in the ring. This has been used to measure emittance growth rates on six bunches of varying intensities in a single store. Also the software supports FFT analysis of turn-by-turn profiles of a single bunch at injection to detect dipole and quadrupole oscillations.

Trace gases are generated by many biological reactions. During anaerobic decomposition, trace levels of hydrogen (H{sub 2}) and carbon monoxide (CO) gases are produced. It was shown previously that these trace gases are intrinsically related to the biochemical reactions occurring and, therefore, offer promise for on-line process monitoring and control. This work was designed to test how effectively hydrogen and CO could be to monitor high-rate anaerobic systems that has significant mass transfer and complex hydraulics. An experimental program was designed to examine the behavior of an upflow anaerobic sludge blanket (UASB) reactor system under steady state and in response to organic loading perturbations. The responses of trace gases CO and H{sub 2} were tracked using an on-line, real-time gas-monitoring system linked to a computer-controlled data acquisition package. Data on conventional process parameters such as pH, chemical oxygen demand (COD), volatile fatty acids (VFAs) were concurrently collected. Monitoring of conventional process indicators (i.e., pH, VFA, gas production) and trace gas (H{sub 2} and CO) indicators was conducted using a matrix of nine different steady-state OLRs (4-23 kg COD/m{sup 3} -d) and system HRTs (0.5 to 2.5 days) was performed to determine any correlation among the indicators. Of OLR, HRT, and influent COD, only OLR had any significant influence on the process indicators examined. All parameters except methane increased with increases in OLR; methane decreased with increased OLR. The OLR and gas production rate (GP) were observed to be linearly correlated.

Results are presented from a study in which a continuously changed gaseous sample was monitored by multiplex gas chromatography (MGC), using the exponential dilution (ED) technique of Ritter and Adams (1976) to change the composition and concentration of a gaseous mixture in such a way as to imitate changes in the atmospheric gases sampled by a descending aircraft. A calibration of the MGC system was performed with four different rates of sample dilution, and the errors resulting from various degrees of change in the sample concentration were determined.

The field of condition monitoring has been an area of rapid growth, with many specialized techniques being developed to measure or predict the health of a particular item of plant. Much of the most recent work has gone into the diagnosis of problems on rotating machines through the application of vibration analysis techniques. These techniques though useful can have a number of limiting factors, such as the need to install specialized sensors and measurement equipment, or the limited scope of the type of data measured. It was recognized in 1992, that the surveillance and condition monitoring procedures available for critical plant, such as gas turbines, were not as comprehensive as they might be and that a novel approach was required to give the operator the necessary holistic view of the health of the plant. This would naturally provide an assessment of the maintenance practices required to yield the highest possible availability without the need to install extensive new instrumentation. From the above objective, the TIGER system was designed which utilizes available data from the gas turbine control system or additionally the plant DCS to measure the behavior of the gas turbine and its associated sub systems. These measured parameters are then compared with an internal model of the turbine system and used to diagnose incorrect responses and therefore the item that is at fault, allowing the operator to quickly restart the turbine after a trip or perform condition based maintenance at the next scheduled outage. This philosophy has been built into the TIGER system and the purpose of this paper is to illustrate its functionality and some of the innovative techniques used in the diagnosis of real gas turbine problems. This is achieved by discussing three case studies where TIGER was integral in returning the plant to operation more quickly than can normally be expected.

Using an asymmetric Lanczos chain algorithm for the calculation of the coupled cluster linear response functions at the coupled cluster singles and doubles (CCSD) and coupled cluster singles and approximate iterative doubles (CC2) levels of approximation, we have calculated the mean excitation energies of the noble gases He, Ne and Ar, and of the hydrogen molecule (H2). Convergence with respect to the one-electron basis set was investigated in detail for families of correlation-consistent basis sets including both augmentation and core-valence functions. We find that the electron correlation effects at the CCSD level change the mean excitation energies obtained at the uncorrelated Hartree-Fock level by about 1%. For the two-electron systems He and H2, our CCSD results (for a Lanczos chain length equal to the full excitation space), I0 = 42.28 eV (helium) and I0 = 19.62 eV (H2), correspond to full configuration interaction results and are therefore the exact, non-relativistic theoretical values for the mean excitation energy of these two systems within the Bethe theory for the chosen basis set and, in the case of H2, at the experimental equilibrium geometry.

The HED (Howardite, Eucrite and Diogenite) group meteorites likely or iginate from the Asteroid 4 Vesta - one of two asteroid targets of NA SA's Dawn mission. Whilst Howardites are polymict breccias of eucriti c and diogenitic material that often contain "regolithic" petrologica l features, neither their exact regolithic nature nor their formation processes are well defined. As the Solar Wind (SW) noblegas compon ent is implanted onto surfaces of solar system bodies, noblegas anal yses of Howardites provides a key indicator of regolithic origin. In addition to SW, previous work by suggested that restricted Ni (300-12 00 micro g/g) and Al2O3 (8-9 wt%) contents may indicate an ancient we ll-mixed regolith. Our research combines petrological, compositional and noblegas analyses to help improve understanding of asteroid reg olith formation processes, which will play an intergral part in the i nterpretation of Dawn mission data. Following compositional and petrological analyses, we developed a regolith grading scheme for our sampl e set of 30 Howardites and polymict Eucrites. In order to test the r egolith indicators suggested by, our 8 selected samples exhibited a r ange of Ni, Al2O3 contents and regolithic grades. Noblegas analyses were performed using furnace stepheating on our MAP 215-50 noblegas mass spectrometer. Of our 8 howardites, only 3 showed evidence of SW noble gases (e.g approaching Ne-20/Ne-22 approximately equals 13.75, Ne-21/Ne-22 approximately equals 0.033). As these samples display low regolithic grades and a range of Ni and Al2O3 contents, so far we are unable to find any correlation between these indicators and "regolit hic" origin. These results have a number of implications for both Ho wardite and Vesta formation, and may suggest complex surface stratigr aphies and surface-gardening processes.

Worldwide research groups are searching for anticancer compounds, many of them are organometalic complexes having platinum group metals as their active centers. Most commonly used cytostatics from this group are cisplatin, carboplatin and oxaliplatin. Cisplatin was used fot the first time in 1978, from this time many platinum derivatives were created. In this review we present biological properties and probable future clinical use of platinum, gold, silver, iridium and ruthenium derivatives. Gold derivative Auranofin has been studied extensively. Action of silver nanoparticles on different cell lines was analysed. Iridium isotopes are commonly used in brachyterapy. Ruthenium compound new anti-tumour metastasis inhibitor (NAMI-A) is used in managing lung cancer metastases. Electroporation of another ruthenium based compound KP1339 was also studied. Most of described complexes have antiproliferative and proapoptotic properties. Further studies need to be made. Nevertheless noble metal based chemotherapheutics and compounds seem to be an interesting direction of research. PMID:26557773

The objective of this program is to develop sensors that allow condition based monitoring of critical combustion parts of gas turbines. Siemens teamed with innovative, small companies that were developing sensor concepts that could monitor wearing and cracking of hot turbine parts. A magnetic crack monitoring sensor concept developed by JENTEK Sensors, Inc. was evaluated in laboratory tests. Designs for engine application were evaluated. The inability to develop a robust lead wire to transmit the signal long distances resulted in a discontinuation of this concept. An optical wear sensor concept proposed by K Sciences GP, LLC was tested in proof-of concept testing. The sensor concept depended, however, on optical fiber tips wearing with the loaded part. The fiber tip wear resulted in too much optical input variability; the sensor could not provide adequate stability for measurement. Siemens developed an alternative optical wear sensor approach that used a commercial PHILTEC, Inc. optical gap sensor with an optical spacer to remove fibers from the wearing surface. The gap sensor measured the length of the wearing spacer to follow loaded part wear. This optical wear sensor was developed to a Technology Readiness Level (TRL) of 5. It was validated in lab tests and installed on a floating transition seal in an F-Class gas turbine. Laboratory tests indicate that the concept can measure wear on loaded parts at temperatures up to 800{degrees}C with uncertainty of < 0.3 mm. Testing in an F-Class engine installation showed that the optical spacer wore with the wearing part. The electro-optics box located outside the engine enclosure survived the engine enclosure environment. The fiber optic cable and the optical spacer, however, both degraded after about 100 operating hours, impacting the signal analysis.

This calc note documents an evaluation of three options for monitoring hydrogen during waste tank intrusive activities. The three options are (1) one Combustible GasMonitor with an operator monitoring the readout, (2) two CGMs with separate operators monitoring each gasmonitor, and (3) one CGM with audible alarm, no dedicated operator monitoring readout. A comparison of the failure probabilities of the three options is provided. This Calculation Note supports the Flammable Gas Analysis for TWRS FSAR and BIO. This document is not to be used as the sole basis to authorize activities or to change authorization, safety or design bases.

The abundance and isotopic composition of helium, neon, argon, krypton, and xenon which were released by stepwise heating of lunar fines (15601.64) and (15271.65) were measured spectrometrically. The results of a composition of noble gases released from the lunar fines with noble gases in meteorites and in the earth are presented along with the isotopic composition of noble gases in lunar fines, in meteorites, and in the atmosphere. A study of two isotopically distinct components of trapped xenon in carbonaceous chondrites is also included.

Metal oxide semiconductor gas sensors are utilised in a variety of different roles and industries. They are relatively inexpensive compared to other sensing technologies, robust, lightweight, long lasting and benefit from high material sensitivity and quick response times. They have been used extensively to measure and monitor trace amounts of environmentally important gases such as carbon monoxide and nitrogen dioxide. In this review the nature of the gas response and how it is fundamentally linked to surface structure is explored. Synthetic routes to metal oxide semiconductor gas sensors are also discussed and related to their affect on surface structure. An overview of important contributions and recent advances are discussed for the use of metal oxide semiconductor sensors for the detection of a variety of gases—CO, NOx, NH3 and the particularly challenging case of CO2. Finally a description of recent advances in work completed at University College London is presented including the use of selective zeolites layers, new perovskite type materials and an innovative chemical vapour deposition approach to film deposition. PMID:22219672

We compare the solar wind (SW) He, Ne, and Ar compositions collected during the Apollo Solar Wind Composition (SWC) experiments (1969-1972; Al- & Pt-foils) and the Genesis mission (2002-2004; so-called DOS targets considered here). While published SW 20Ne/22Ne and 36Ar/38Ar ratios of both data sets agree, differences exist in the 4He/3He, 4He/20Ne, and 20Ne/36Ar ratios. However, 20Ne/36Ar ratios from Apollo-16 Pt-foils, exclusively adopted as SW values by the SWC team, are consistent with the Genesis results. We investigate if the differences indicate a variability of the SW over the course of about 30 yr, or systematic biases of the two data sets, which were collected in different environments and measured several decades apart in different laboratories (University of Bern; ETH Zurich). New measurements of Apollo-15 SWC aluminum foils in Zurich generally agree with the original measurements performed in Bern. Zurich samples show slightly lower 4He concentrations suggesting a few percent of diffusive loss of 4He during storage of the foils. A 3% difference between the He isotopic ratios measured in Bern and in Zurich possibly represents an analytical bias between the laboratories. The low SW 4He/20Ne and 20Ne/36Ar ratios in Apollo-15 Al-foils compared to Genesis data are consistent with a mixture of Genesis-like SW and noble gases from small amounts of lunar dust. Our data suggest that the mean SW He, Ne, and Ar isotopic and elemental compositions have not significantly changed between the overall Apollo and Genesis mission collection periods.

We developed a new fluid property module for TOUGH2, called EOSN, to simulate transport of noble gases in the subsurface. Currently, users may select any of five different noble gases as well as CO2, two at a time. For the three gas components (air and two user-specified noble gases) in EOSN, the Henry's coefficients and the diffusivities in the gas phase are no longer assumed constants, but are temperature dependent. We used the Crovetto et al. (1982) model to estimate Henry's coefficients, and the Reid et al. (1987) correlations to calculate gas phase diffusivities. The new module requires users to provide names of the selected noble gases, which properties are provided internally. There are options for users to specify any (non-zero) molecular weights and half-lives for the gas components. We provide two examples to show applications of TOUGH2IEOSN. While temperature effects are relatively insignificant for one example problem where advection is dominant, they cause almost an order of magnitude difference for the other case where diffusion becomes a dominant process and temperature variations are relatively large. It appears that thermodynamic effects on gas diffusivities and Henry's coefficients can be important for low-permeability porous media and zones with large temperature variations.

Water-soluble fluorescent metallic clusters at sizes comparable to the Fermi wavelength of an electron (˜0.5 nm for gold and silver) were created and their photophysical properties were investigated at the bulk and single molecule levels. We employed biocompatible dendrimer and peptide to prepare a series of strong fluorescent gold and silver clusters with chemical or photo reduction methods. Facilitated by the well-defined dendrimer size, electrospray ionization mass spectrometry indicates that the fluorescent silver nanocluster size ranges from 2 to 8 Ag atoms. The correlation of emission energy with the number of atoms, N, in each gold nanocluster is quantitatively fit for the smallest nanoclusters with no adjustable parameters by the simple scaling relation of EFermi/N1/3, in which EFermi is the Fermi energy of bulk gold. The transition energy scaling inversely with cluster radius indicates that electronic structure can be well described with the spherical jellium model and further demonstrates that these nanomaterials are "multi-electron artificial atoms". Fluorescence from these small metal clusters can be considered protoplasmonic, molecular transitions of the free conduction electrons before the onset of collective dipole oscillations occurring when a continuous density of states is reached. In addition, very strong single molecular Stokes and anti-Stokes Raman enhancement by fluorescent silver clusters was observed. Pushing to larger sizes, we also created ˜2nm diameter glutathione encapsulated luminescent gold nanoparticles. Distinct from similarly sized but nonluminescent gold nanoparticles, these 2 nm gold nanoparticles show bright, long lifetime emission but no plasmon absorption. The emission might arise from charge transfer between gold atoms and the thiol ligand. Providing the "missing link" between atomic and nanoparticle behavior in noble metals, these highly fluorescent, water-soluble gold and silver nanoclusters offer complementary transition

Analytical instruments based on cavity ring-down spectroscopy (CRDS) with automated calibration systems are being deployed on South Atlantic Islands to monitor atmospheric CO2 and CH4. Data have been returned daily from the CRDS analyzer deployed at the Meteorological Office Ascension Island site since 22 June 2010. Installation of a second instrument near Stanley Airport on the Falkland Islands is due to take place in October 2010. The equipment will reach the Falklands on the British Antarctic Survey ship, James Clark Ross and will monitor CO2 and CH4 continuously on the Atlantic voyage from the UK, providing additional important greenhouse gas data for the South Atlantic as well as for the south and east coast of the UK. Data for Ascension Island winter (June to August) show variations in CO2 between 387 and 390 ppm and CH4 between 1760 and 1778 ppb, but with prolonged periods of 3 weeks or more with both gas species toward the upper or lower ends of these ranges. These trends are also observed in twice weekly NOAA flask samples collected within 100 m of the RHUL air inlet. The averaged mixing ratio for NOAA flask samples collected over this period is within 0.04 ppm for CO2 and 0.4 ppb for CH4 of the averaged continuous CRDS record. Data for δ13C of methane measured on flask samples collected by RHUL since 2000 show a range of -47.2 to -46.7‰ with a maximum seasonal cycle of 0.3‰. Comparison of RHUL data for 2000-2004 and 2009-2010 suggest an isotopic enrichment of 0.2 per mil associated with an increase in mixing ratio of 15-20 ppb over this period.

Software for monitoring and evaluating the performance of gas turbines is being developed under the auspices of Gas Research Institute (GRI). This paper describes the PEGASUS software and monitoring system. PEGASUS is an acronym for Performance Evaluation of GAS Users Systems. Field test results, on multi-shaft turbines used in the gas pipeline industry, have demonstrated the potential of the software. The software and instrumentation, can help identify maintenance and upgrade actions to improve performance.

The chemical differences between deep- and shallow-mantle sources of oceanic basalts provide evidence that several distinct components coexist within the Earth's mantle. Most of these components have been identified as recycled in origin. However, the noble-gas signature is still a matter of debate and questions the preservation of primitive regions in the convective mantle. We show that a model where the noble-gas signature observed in Hawaii and Iceland comes from a pristine homogeneous deep layer would imply a primitive (3)He content and (3)He/(22)Ne ratio that are very unlikely. On the contrary, mass balances show that the partly degassed peridotite of a marble-cake mantle can be the noble-gas end-member with an apparent 'primitive'-like composition. This component is mixed with recycled oceanic crust in different proportions in the plume sources and in the shallow mantle. A recycling model of the mantle, involving gravitational segregation of the oceanic crust at the bottom of the mantle, potentially satisfies trace-element as well as noble-gas constraints. PMID:12460484

Animal facilities produce large amounts of harmful gases such as ammonia, hydrogen sulfide, and methane, many of which have a pungent odor. The harmful gases produced by animal housing not only affect the health of people and livestock but also pollute the air. The detection of the harmful gases can effectively improve efficiency of livestock production and reduce environmental pollution. More and more optical detection methods are applied to the detection of the harmful gases produced by animal housing. This summarizes optical detection methods for monitoring the harmful gases in animal housing recently, including nondispersive infrared gas analyzer, ultraviolet differential optical absorption spectroscopy, Fourier transform infrared spectroscopy, and tunable diode laser absorption spectroscopy. The basic principle and the characteristics of these methods are illustrated and the applications on the detection of harmful gases in animal housing are described. Meanwhile, the research of harmful gases monitoring for livestock production based on these methods were listed. The current situation and future development of the detection methods for harmful gases generated by animal housing were summarized by comparing the advantages and disadvantages of each method.

Chikyu Expedition 319 was the first cruise of the Integrated Ocean Drilling Program (IODP) where riser drilling was performed and real-time mud gasmonitoring was conducted, because this technique requires drill-mud circulation. In contrast to conventional IODP drilling that uses drill water in combination with lost circulation, during riser drilling the drill mud returns back to the surface through a riser pipe which encases the drill pipe. The dissolved gas is extracted from returning drill mud, analyzed in real time and sampled for noblegas and stable isotopes studies. This technique has been applied in the past on scientific continental drilling projects of e.g. the International Continental Drilling Program. Expedition 319 is part of the NanTroSEIZE project, a multiexpedition, multistage IODP drilling program focused on understanding the mechanics of seismogenesis and ruptures propagation along the Nankai accretionary prism. Riser drilling was carried out on Hole C0009 that intersects the cover sediments of the Kumano Basin and probably penetrates into the accretionary prism below. Site NT2-11 is located approx. 60 km SE of the harbour of Shingu, Japan. Real-time mud gasmonitoring was performed in Hole C0009 during drilling from 703 mbsf (meter below sea floor) down to 1594 mbsf and during hole enlargement from 703 mbsf to 1569 mbsf. Both datasets show similar gas distribution at depth. Gas was furthermore extracted, sampled and analyzed from drill cuttings. Drill mud gas is generally composed of air and gases that derive from the formation. The principal formation gas in drill mud from both drilling phases and in cuttings was methane. Up to 14 vol % CH4 was detected during drilling and up to 3 vol % during hole enlargement. Down to 800 mbsf and below 1280 mbsf, the methane concentration in drill mud is lower than in the surrounded interval, where methane peaks at several depths. At 1280 mbsf an unconformity is indicated from lihology, in seismic and

Impurity deposition and mixing during gas jet-initiated plasma shutdown is studied using a rapid ({approx}2 ms), massive ({approx}10{sup 22} particles) injection of neon or argon into stationary DIII-D H-mode discharges. Fast-gated camera images indicate that the bulk of the jet neutrals do not penetrate far into the plasma pedestal. Nevertheless, high ({approx}90%) thermal quench radiated power fractions are achieved; this appears to be facilitated through a combination of fast ion mixing and fast heat transport, both driven by large-scale MHD activity. Also, runaway electron suppression is achieved for sufficiently high gas jet pressures. These experiments suggest that massive gas injection could be viable for disruption mitigation in future tokamaks even if core penetration of jet neutrals is not achieved.

Several noble gases, although classified as inert substances, exert a tissue-protective effect in different experimental models when applied before organ ischaemia as an early or late preconditioning stimulus, after ischaemia as a post-conditioning stimulus or when given in combination before, during and/or after ischaemia. A wide range of organs can be protected by these inert substances, in particular cardiac and neuronal tissue. In this review we summarize the data on noblegas-induced cardioprotection, focusing on the underlying protective mechanisms. We will also look at translatability of experimental data to the clinical situation. PMID:25363501

The conversion of methane is measured in a planar-type dielectric barrier discharge reactor using three different noble gases—He, Ne, and Ar—as additives. The empirical results obtained clearly indicate that methane activation is considerably affected by thy type of noblegas used. Through 0-D calculations, the discharge parameters inside the reactor, i.e., electron temperature and electron density, are estimated using experiment results. A comparison of the discharge characteristics and experimental results shows that the electron temperature is an important factor in achieving high methane activation and the mixture with Ar gas shows the highest methane conversion. These results are constructed using the mechanisms of energy and charge transfer from excited and ionized noblegas atoms to methane molecules, considering the number density of active atoms of noble gases. Finally, electron temperatures obtained for gas mixtures having different reactant compositions and concentrations are analyzed to estimate methane activation.

Mantle noble gases record important and ancient isotopic heterogeneities, which fundamentally influence our understanding of mantle geodynamics, yet these heterogeneities are difficult to fully interpret without understanding the basic mechanisms of noblegas storage and transport in mantle minerals. A series of annealing experiments that mimic mantle conditions (i.e. sub-solidus with natural, polycrystalline, texturally equilibrated olivines at low noblegas partial pressures) show that intergranular interfaces (grain boundaries) are major hosts for noble gases in the mantle, and that interfaces can dramatically fractionate noble gases from their radio-parents (U + Th and K). Therefore, noblegas isotopic heterogeneities in the mantle could result from grain size variations. Fine-grained lithologies (mylonites and ultramylonites, for example) with more grain boundaries will have lower U/3He ratios (compared to a coarse grained equivalent), which, over time, will preserve higher 3He/4He ratios. As predicted by theory of points defect diffusivity, these results show that noblegas diffusion along interfaces is different from those in the grain lattice itself at low temperatures. However, for grain size relevant of the Earth's mantle, the resulting effective correlated activation energies (Ea) and pre-exponential factors (Do /a2) produce similar diffusivities at mantle temperatures for interface- and lattice-hosted helium. Therefore, grain boundaries do not significantly affect helium transport at mantle conditions and length scales.

Grasslands in Central Europe are of enormous social, ecological and economical importance. They are intensively managed, but the influence of different common practices (i.e. fertilization, harvesting) on the total greenhouse gas budget of grasslands is not fully understood, yet. In addition, it is unknown how these ecosystems will react due to climate change. Increasing temperatures and changing precipitation will likely have an effect on productivity of grasslands and on bio-geo-chemical processes responsible for emissions of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O). In the frame of the TERENO Project (www.tereno.net), a long-term observatory has been implemented in the Ammer catchment, southern Germany. Acting as an in situ global change experiment, 36 big lysimeters (1 m2 section, 150 cm height) have been translocated along an altitudinal gradient, including three sites ranging from 600 to 860 meters above sea level. In addition, two treatments have been considered, corresponding to different management intensities. The overall aim of the pre-alpine TERENO observatory is improving our understanding of the consequences of climate change and management on productivity, greenhouse gas balance, soil nutritional status, nutrient leaching and hydrology of grasslands. Two of the sites are equipped with a fully automated measurement system in order to continuously and accurately monitor the soil-atmosphere greenhouse gas exchange. Thus, a stainless steel chamber (1 m2 section, 80 cm height) is controlled by a robotized system. The chamber is hanging on a metal structure which can move both vertically and horizontally, so that the chamber is able to be set onto each of the lysimeters placed on the field. Furthermore, the headspace of the chamber is connected with a gas tube to a Quantum Cascade Laser, which continuously measures CO2, CH4, N2O and H2O mixing ratios. The chamber acts as a static chamber and sets for 15 minutes onto each lysimeter

Oldonyo Lengai,Tanzania, is the only volcano on Earth that is actively erupting carbonatitic lavas. In order to further constrain the origin of the Oldonyo Lengai magmas, an expedition to Oldonyo Lengai in July 2005 sampled to volcanic gases. Two fumaroles were sampled, one with a discharging temperature of 124 °C, the other more than 168 °C. The chemical composition of discharging gases is dominated by H2O (approx77 mol%) and CO2 (approx 22 mol%), SO2, H2S and HCl make up less than 1 mol%, combined. The inert gases (N2, He, He/Ne) show that these samples contain virtually no air. He/Ne ratios are between 2000 and 6500 and He/Ar ratios are up to 0.3 [Fischer et al, 2006, this volume]. The 3He/4He ratio of 6.7 - 6.8 Ra is consistent with an upper mantle origin of these gases. We have also measured Ne and Xe isotopic compositions of several aliquots of the sampled gases using a multicollector noblegas mass spectrometer (HELIX-MC). The additional precision afforded by multicollection allows us to identify noblegas isotopic anomalies at the sub 5 per mil level. Despite the excellent purity (low atmospheric content) of the gases, as evidenced by extremely high He/Ne ratios, the isotopic compositions of both Ne and Xe are very close to those of the atmosphere: a 2 per mil excess in 129Xe/130Xe ratio was observed (the remaining Xe isotope ratios being indistinguishable from air) and 20Ne/22Ne up to 10.3 was measured (50 per mil higher than air) in a split of the sample that has He/Ne = 6500. Although isotolically anomalous Ne was observed, it is not possible to determine if this is indeed mantle - derived Ne or if the 20Ne excesses result from kinetic fractionationed air entrained within the volcano's plumbing system: the composition of the three Ne isotopes (20Ne, 21Ne and 22Ne) are consistent with mass fractionation processes. Our results are most readily interpreted as atmospheric entrainment prior to sampling. However, further measurements of the remaining noble

This paper presents the global network, NOVAC (Network for Observation of Volcanic and Atmospheric Change), aiming at automatic gas emission monitoring at active volcanoes worldwide. Data from the network will primarily be used for volcanic risk assessment but also for geophysical research, studies of atmospheric change and ground validation of satellite instruments. A novel type of instrument, the Scanning miniaturized Differential Optical Absorption Spectroscopy (mini-DOAS) instrument, is applied in the network to measure volcanic gas emissions by UV absorption spectroscopy. The instrument is set up 5-10 km downwind of the volcano under study and typically 2-4 instruments are deployed at each volcano in order to cover different wind directions and facilitate measurements of plume height and plume direction. Two different versions of the instrument have been developed. Version I was designed to be a robust and simple instrument for measurement of volcanic SO2 emissions at high time-resolution with minimal power consumption. Version II was designed to allow the best possible spectroscopy, and enhanced flexibility in regard to measurement geometry at the cost of larger complexity, power consumption and price. In the paper the project is described as well as the developed software, the hardware of the two instrument versions, measurement strategies, data communication and archiving routines. As of December 2008 a total of 46 instruments have been installed at 18 volcanoes worldwide. As a typical example the installation at Tungurahua Volcano in Ecuador is described, together with some results from the first 21 months of operation at this volcano.

This report documents the measurement of headspace gas concentrations and monitoring results from the Hanford tanks that have continuous flammable gasmonitoring. The systems used to monitor the tanks are Standard Hydrogen Monitoring Systems. Further characterization of the tank off-gases was done with Gas Characterization Systems and vapor grab samples. The background concentrations of all tanks are below the action level of 6250 ppm. Other information which can be derived from the measurements (such as generation rate, release rate, and ventilation rate) is also discussed.

This report documents the measurement of headspace gas concentrations and monitoring results from the Hanford tanks that have continuous flammable gasmonitoring. The systems used to monitor the tanks are Standard Hydrogen Monitoring Systems. Further characterization of the tank off-gases was done with Gas Characterization systems and vapor grab samples. The background concentrations of all tanks are below the action level of 6250 ppm. Other information which can be derived from the measurements (such as generation rate, released rate, and ventilation rate) is also discussed.

... AGENCY 40 CFR Part 98 RIN 2060-AR74 Greenhouse Gas Reporting Rule: Revision to Best Available Monitoring... natural gas systems source category of the Greenhouse Gas Reporting Rule must submit requests for use of... timely withdrawal notice in the Federal Register to inform the public that this rule will not take...

Xenon is an anesthetic with minimal hemodynamic side effects, making it an ideal agent for cardiocompromised patients. We investigated if xenon induces pharmacological preconditioning (PC) of the rat heart and elucidated the underlying molecular mechanisms. For infarct size measurements, anesthetized rats were subjected to 25 min of coronary artery occlusion followed by 120 min of reperfusion. Rats received either the anesthetic gas xenon, the volatile anesthetic isoflurane or as positive control ischemic preconditioning (IPC) during three 5-min periods before 25-min ischemia. Control animals remained untreated for 45 min. To investigate the involvement of protein kinase C (PKC) and p38 mitogen-activated protein kinase (MAPK), rats were pretreated with the PKC inhibitor calphostin C (0.1 mg kg−1) or the p38 MAPK inhibitor SB203580 (1 mg kg−1). Additional hearts were excised for Western blot and immunohistochemistry. Infarct size was reduced from 50.9±16.7% in controls to 28.1±10.3% in xenon, 28.6±9.9% in isoflurane and to 28.5±5.4% in IPC hearts. Both, calphostin C and SB203580, abolished the observed cardioprotection after xenon and isoflurane administration but not after IPC. Immunofluorescence staining and Western blot assay revealed an increased phosphorylation and translocation of PKC-ɛ in xenon treated hearts. This effect could be blocked by calphostin C but not by SB203580. Moreover, the phosphorylation of p38 MAPK was induced by xenon and this effect was blocked by calphostin C. In summary, we demonstrate that xenon induces cardioprotection by PC and that activation of PKC-ɛ and its downstream target p38 MAPK are central molecular mechanisms involved. Thus, the results of the present study may contribute to elucidate the beneficial cardioprotective effects of this anesthetic gas. PMID:15644876

Potential natural gas leakage into shallow, overlying formations and aquifers from Marcellus Shale gas drilling operations is a public concern. However, before natural gas could reach underground sources of drinking water (USDW), it must pass through several geologic formations. Tracer and pressure monitoring in formations overlying the Marcellus could help detect natural gas leakage at hydraulic fracturing sites before it reaches USDW. In this study, a numerical simulation code (TOUGH 2) was used to investigate the potential for detecting leaking natural gas in such an overlying geologic formation. The modeled zone was based on a gas field in Greene County, Pennsylvania, undergoing production activities. The model assumed, hypothetically, that methane (CH4), the primary component of natural gas, with some tracer, was leaking around an existing well between the Marcellus Shale and the shallower and lower-pressure Bradford Formation. The leaky well was located 170 m away from a monitoring well, in the Bradford Formation. A simulation study was performed to determine how quickly the tracer monitoring could detect a leak of a known size. Using some typical parameters for the Bradford Formation, model results showed that a detectable tracer volume fraction of 2.0 × 10(-15) would be noted at the monitoring well in 9.8 years. The most rapid detection of tracer for the leak rates simulated was 81 days, but this scenario required that the leakage release point was at the same depth as the perforation zone of the monitoring well and the zones above and below the perforation zone had low permeability, which created a preferred tracer migration pathway along the perforation zone. Sensitivity analysis indicated that the time needed to detect CH4 leakage at the monitoring well was very sensitive to changes in the thickness of the high-permeability zone, CH4 leaking rate, and production rate of the monitoring well. PMID:25144442

This work explores the application of the liquid scintillation counting of polycarbonates for measurement of the activity concentration of radioactive noble gases. Results from experimental studies of the method are presented. Potential applications in the monitoring of radioactive noble gases are discussed. PMID:24559941

Due consideration of the probable history of the Martian atmosphere, as well as noble-gas data from the Mars-derived SNC meteorites and from laboratory tests on the trapping of noble gases in ice, are the bases of the presently hypothesized domination of noble gases in the atmospheres of all terrestrial planets by a mixture of internal components and a contribution from comets. If verified, this hypothesis would underscore the significance of impacts for these planets' volatile inventories. The sizes of the hypothesized comets are of the order of 120 km for Venus and only 80 km for that which struck the earth.

Carbonatitic melts have been identified in the earth’s upper mantle and experimental evidence suggests that such melts are stable at mantle conditions. Due to high carbonatite/silicate partition coefficients for certain trace elements, and due to the low melting points, low viscosities and low dihedral angles of carbonatite liquids, these liquids play a significant role in trace element fractionation in the mantle. However, the solubilities of the noble gases in carbonatitic liquids are poorly constrained although initial data at low pressure (1 bar) surprisingly suggest that the noble gases are poorly soluble in carbonatite liquids [1]. Partitioning of noble gases relative to the parents of radiogenic noble gases - primarily U, Th and K - has consequences for the isotopic evolution of mantle noble gases, consequently determination of noblegas solubilities in carbonatite phases is of extreme interest for mantle geodynamics. Two-liquid experimental charges consisting of nephelenite and Na2CO3 were synthesized at 1145 C and pressures between 0.6 and 2.5 GPa in sealed Au-Pd capsules in a piston cylinder apparatus. The experimental runs were c. 12h in duration and the charges were quenched at >200 C min-1 to form two immiscibly separated glasses phases. The nephelenite glass starting material had been saturated with a noblegas mixture (0.5 He, 0.02 Ne, 0.48 Ar) prior to synthesis. This procedure introduced noble gases without creating a free gas phase. The noble gases (He and Ar only) were measured in 3 stages: 1) the capsule was pierced under vacuum and the ‘free gas’ residing in the capsule pore space was analysed; 2) the entire capsule was heated to 250 C and the gases liberated were analysed and 3) the nephelenite glass was melting by a CO2 laser and the gases liberated analysed. The first stage of the analysis was to measure any noble gases (principally He) that may have diffused out of the carbonatite during the quench or between the period (of a few

In recent years, the USGS Volcano Hazards Program has worked to implement continuous real-time in situ volcanic gasmonitoring at volcanoes in the Cascade Range and Alaska. The main goal of this ongoing effort is to better link the compositions of volcanic gases to other real-time monitoring data, such as seismicity and deformation, in order to improve baseline monitoring and early detection of volcanic unrest. Due to the remote and difficult-to-access nature of volcanic-gasmonitoring sites in the Cascades and Alaska, we developed Multi-GAS instruments that can operate unattended for long periods of time with minimal direct maintenance from field personnel. Our Multi-GAS stations measure H2O, CO2, SO2, and H2S gas concentrations, are comprised entirely of commercial off-the-shelf components, and are powered by small solar energy systems. One notable feature of our Multi-GAS stations is that they include a unique capability to perform automated CO2, SO2, and H2S sensor verifications using portable gas standards while deployed in the field, thereby allowing for rigorous tracking of sensor performances. In addition, we have developed novel onboard data-processing routines that allow diagnostic and monitoring data - including gas ratios (e.g. CO2/SO2) - to be streamed in real time to internal observatory and public web pages without user input. Here we present over one year of continuous data from a permanent Multi-GAS station installed in August 2014 in the crater of Mount St. Helens, Washington, and several months of data from a station installed near the summit of Augustine Volcano, Alaska in June 2015. Data from the Mount St. Helens Multi-GAS station has been streaming to a public USGS site since early 2015, a first for a permanent Multi-GAS site. Neither station has detected significant changes in gas concentrations or compositions since they were installed, consistent with low levels of seismicity and deformation.

In aquatic systems noble gases, radon, and bio-geochemically conservative transient trace gases (SF6, CFCs) are frequently applied to determine water residence times and to reconstruct past environmental and climatic conditions. Recent experimental breakthroughs now enable ● to apply the well-established concepts of terrestrial noblegas geochemistry in waters to the minute water amounts stored in sediment pore space and in fluid inclusions (A), ● to determine gas exchange processes on the bio-geochemical relevant time scales of minutes - hours (B), and ● to separate diffusive and advective gas transport in soil air (C). A. Noble-gas analysis in water samples (< 1 g) facilitates determining the solute transport in the pore space and identifying the origin of bio- and geogenic fluids in (un) consolidated sediments [1]. Advanced techniques that combine crushing and sieving speleothem samples in ultra-high-vacuum to a specific grain size allow to separate air and water-bearing fluid inclusions and thus enables noble-gas-based reconstruction of environmental conditions from water masses as small as 1mg [2]. B. The coupling of noblegas analysis with approaches of gas chromatography permits combined analysis of noble gases and other gases species (e.g., SF6, CFCs, O2, N2) from a single water sample. The new method substantially improves ground water dating by SF6 and CFCs as excess air is quantified from the same sample and hence can adequately be corrected for [3]. Portable membrane-inlet mass spectrometers enable the quasi-continuous and real-time analysis of noble gases and other dissolved gases directly in the field, allowing, for instance, quantification of O2 turnover rates on small time scales [4]. C. New technical developments perfect 222Rn analysis in water by the synchronous the determination of the short-lived 220Rn. The combined 220,222Rn analysis sheds light on the emanation behaviour of radon by identifying soil water content to be the crucial

This is the final report of a six-month, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The nuclei of noble gases can be hyper polarized through a laser-driven spin exchange to a degree many orders of magnitude larger than that attainable by thermal polarization without requiring a strong magnetic field. The increased polarization from the laser pumping enables a good nuclear magnetic resonance (NMR) signal from a gas. The main goal of this project was to demonstrate diffusion-weighted imaging of such hyper-polarized noblegas with magnetic resonance imaging (MRI). Possible applications include characterizing porosity of materials and dynamically imaging pressure distributions in biological or acoustical systems.

Electric conduction in titanium dioxide is known to be oxygen sensitive and the conductivity of a TiO2 ceramic body is determined mainly by the concentration of its naturally occurring oxygen vacancy. Recently, fabrications and electronic features of a number of noble metal/TiO2-based electronic devices, such as solar cells, UV detectors, gas sensors and memristive devices have been demonstrated. Here, we investigate the effect of oxygen adsorption at the noble metal/TiO2 junction in such devices, and show the potentials of these junctions in chemical sensor fabrication. The polycrystalline, poly-phase TiO2 layers are grown by the selective and controlled oxidation of titanium thin films vacuum deposited on silica substrates. Noble metal thin films are deposited on the oxide layers by physical vapor deposition. Current-voltage (I-V) diagrams of the fabricated devices are studied for Ag/, Au/, and Pt/TiO2 samples. The raw samples show no junction energy barrier. After a thermal annealing in air at 250° C, I-V diagrams change drastically. The annealed samples demonstrate highly non-linear I-V indicating the formation of high Schottky energy barriers at the noble metal/TiO2 junctions. The phenomenon is described based on the effect of the oxygen atoms adsorbed at the junction.

The Murchison carbonaceous chondrite contains three isotopically anomalous noble-gas components of apparently presolar origin: two kinds of Ne-E, (Ne-20)/(Ne-22) less than 0.6, and s-process Kr + Xe (enriched in the even isotopes 82, 84, 86, 128, 130, 132). Their carriers are tentatively identified as spinel and two carbonaceous phases, the principal high-temperature stellar condensates at low and high C/O ratios, respectively.

A system developed by NASA has been used for monitoring air quality around different locations. The system was designed for aircraft applications but has proven to be very useful as a portable gas analyzer. The system has been used to monitor air quality around volcanoes, cities, and the surrounding areas. The transport of the system has been via aircraft, car, and hand carried.

The stability of Ng{sub n}@B{sub 12}N{sub 12} and Ng{sub n}@B{sub 16}N{sub 16} systems is assessed through a density functional study and ab initio simulation. Although they are found to be thermodynamically unstable with respect to the dissociation of individual Ng atoms and parent cages, ab initio simulation reveals that except Ne{sub 2}@B{sub 12}N{sub 12} they are kinetically stable to retain their structures intact throughout the simulation time (500 fs) at 298 K. The Ne{sub 2}@B{sub 12}N{sub 12} cage dissociates and the Ne atoms get separated as the simulation proceeds at this temperature but at a lower temperature (77 K) it is also found to be kinetically stable. He-He unit undergoes translation, rotation and vibration inside the cavity of B{sub 12}N{sub 12} and B{sub 16}N{sub 16} cages. Electron density analysis shows that the He-He interaction in He{sub 2}@B{sub 16}N{sub 16} is of closed-shell type whereas for the same in He{sub 2}@B{sub 12}N{sub 12} there may have some degree of covalent character. In few cases, especially for the heavier Ng atoms, the Ng-N/B bonds are also found to have some degree of covalent character. But the Wiberg bond indices show zero bond order in He-He bond and very low bond order in cases of Ng-N/B bonds. The energy decomposition analysis further shows that the ΔE{sub orb} term contributes 40.9% and 37.3% towards the total attraction in the He{sub 2} dimers having the same distances as in He{sub 2}@B{sub 12}N{sub 12} and He{sub 2}@B{sub 16}N{sub 16}, respectively. Therefore, confinement causes some type of orbital interaction between two He atoms, which akins to some degree of covalent character.

Atmospheric noble gases (e.g., 22Ne, 36Ar, 84Kr, 130Xe) are introduced into the subsurface by recharge water in solubility equilibrium with the atmosphere (Air Saturated Water - ASW). Because noble gases are chemically inert and stable in nature, they are only sensitive to subsurface physical processes. More specifically, depletion of this component in sedimentary systems commonly suggests loss to an oil or natural gas phase in the subsurface, which is originally free of atmospheric noble gases. This has been traditionally used to identify and quantify subsurface oil, gas, and water phase interactions. Alternatively, depletion of atmospheric noble gases due to subsurface boiling and steam phase separation has also been previously recorded in tectonically active areas (hydrothermal systems). Such depletion is thus indicative of the occurrence of a thermal event and can be used to trace the thermal history of stable tectonic regions. Here, we present noblegas concentrations of 38 deep brines (~0.5-3.6km) from the Michigan Basin. The atmospheric noblegas component shows a strong depletion pattern with respect to air saturated water. Depletion of lighter gases (22Ne and 36Ar) is stronger compared to the heavier ones (84Kr and 130Xe). To understand the mechanisms responsible for this overall atmospheric noblegas depletion, phase interaction models were tested. We show that this atmospheric noblegas depletion pattern is best explained by a model involving subsurface boiling and steam separation, and thus, consistent with the occurrence of a past thermal event of mantle origin as previously indicated by both high 4He/heat flux ratios and the presence of primordial mantle He and Ne signatures in the basin. Such a conceptual model is also consistent with the presence of past elevated temperatures in the Michigan Basin (e.g., ~80- 260°C) at shallow depths as suggested by previous thermal studies in the basin. We suggest that recent reactivation of the ancient mid

Montgomery Watson was retained by the Bonneville Power Administration to evaluate the monitoring program for gas bubble disease signs and dissolved gas supersaturation levels on the Columbia and Snake rivers. The results of this evaluation will provide the basis for improving protocols and procedures for future monitoring efforts. Key study team members were Dr. John Colt, Dr. Larry Fidler, and Dr. Ralph Elston. On the week of June 6 through 10, 1994 the study team visited eight monitoring sites (smolt, adult, and resident fish) on the Columbia and Snake rivers. Additional protocol evaluations were conducted at the Willard Field Station (National Biological Survey) and Pacific Northwest Laboratories at Richland (Battelle). On June 13 and 14, 1994, the study team visited the North Pacific Division office of the U.S. Corps of Engineers and the Fish Passage Center to collect additional information and data on the monitoring programs. Considering the speed at which the Gas Bubble Trauma Monitoring Program was implemented this year, the Fish Passage Center and cooperating Federal, State, and Tribal Agencies have been doing an incredible job. Thirty-one specific recommendations are presented in this report and are summarized in Section 14.

Gas insulated substations (GIS) are very reliable; but when a short circuit occurs, finding the fault so that equipment can be repaired can take a long time. Infrared (IR) fault location techniques offer some promise to enable faster fault location in the future. It can be very time consuming to locate a short circuit inside a gas insulated bus segment of a gas insulated substation. Special testing may be required, and holes may have to be cut in order to locate the fault so that repair can be initiated. This process is not only expensive but can also lead to damage of unfaulted parts and contamination of the system, which can degrade its reliability. Fast and simple identification of the fault location is highly desirable for reliable operation of the substation. Earlier work had indicated that IR techniques could meet functional requirements and might be cost effective for this application.

Models that trace the origin of noble gases in the atmospheres of the terrestrial planets (Venus, Earth and Mars) to the 'planetary component' in chondritic meteorites confront several problems. The 'missing' xenon in the atmospheres of Mars and Earth is one of the most obvious; this gas is not hidden or trapped in surface materials. On Venus, the absolute abundances of neon and argon per gram of rock are higher even than those in carbonaceous chondrites, whereas the relative abundances of argon and krypton are closer to solar than to chondritic values (there is only an upper limit on xenon). Pepin has developed a model that emphasizes hydrodynamic escape of early, massive hydrogen atmospheres to explain the abundances and isotope ratios of noble gases on all three planets. We have previously suggested that the unusual abundances of heavy noble gases on Venus might be explained by the impact of a low-temperature comet. Further consideration of the probable history of the martian atmosphere, the noble-gas data from the (Mars-derived) SNC meteorites and laboratory experiments on the trapping of noble gases in ice lead us to propose here that the noble gases in the atmospheres of all of the terrestrial planets are dominated by a mixture of an internal component and contribution from impacting icy planetesimals (comets). If true, this hypothesis illustrates the importance of impacts in determining the volatile inventories of these planets. PMID:11536499

Primary Goal of this project is to (1) Design/build a flexible system to monitor air contamination (2) Learn requirements for operating system in low pressure and low temperature environments (3) Design/build system for integration into aircraft and automobiles Secondary Goals/Offshoots are (1) Fly aboard different aircraft (2)Hand-carry unit (3) Drive unit in automobiles.

Underground natural Gas Storage (UGS) can balance the gas demand and supply through injecting gas into or withdraw gas from the subsurface rock formation. UGS has been wildly established all over the world to face the complicated international energy system. In 2013, the Hutubi underground natural gas storage was put into production, which was one of the largest UGS in China. In the Hutubi UGS, the pressurized natural gas is injected into and extracted from an obsolete gas reservoir during summer and winter time, respectively. The repeatable in and out going high pressure gas may change the stress state and material properties of the underground rock formation, which may in turn cause surface deformation and alter the seismic hazard in this region. To understand the physical process of the periodic loading and unloading, we established a multi-disciplinary monitoring system composed of a geodetic network, a seismic network, and an active source monitoring system. The position and level of 13 spots around and above the UGS area are measured every three to six months with Global Position System (GPS) and short base-line leveling. More than 30 portable broad band three component seismic stations were deployed in study area to continuously monitor the background and possible triggered seismicity. These seismic stations together with a 12000 in3 airgun source, are also used to monitor the seismic velocity change associated with the gas injection and extraction. Preliminary results indicate that seismic velocity change correlates well with the injection pressure; seismicity decays with the lapse time after the startup of Hutubi UGS; small but detectable surface deformation associated with the gas activities is observed.

Over the past few years, hydraulic fracturing and horizontal drilling techniques have been extensively used to extract shale gas from the Marcellus Shale. Likewise, several environmental violations that have been repeatedly reported in drilling sites have created greater awareness on potentially adverse environmental impacts of shale gas. Long-term monitoring in the Marcellus Shale is the key to maintain and improve the quality of water supplies in future. Currently, the absence of an efficient water quality monitoring network prevents the detection and source identification of contaminants associated with shale gas activities. Evaluation and re-design of monitoring networks from time to time is a major step towards efficient water resources planning and management. In this study, we assessed the performance of the current water quality monitoring network with respect to the shale gas development in Pennsylvania. For better evaluation, the Oil and Gas Compliance Report by the Pennsylvania Department of Environmental Protection between January 2005 and May 2013 was compiled. Using statistical and GIS methods each violation item was examined against the number and location of sensors in the current monitoring network. The results helped identify the adequacy of the number of sensors to detect the potential contamination. Moreover, to improve the performance and to lower the long-term monitoring costs, we re-designed the network using optimization methods. This optimal system maximizes the understanding of the aquifer condition and investigates the shale gas industry impacts on shallow aquifers, and it is applicable to other watersheds with shale oil and gas drilling activities.

This document has been developed for the nontechnical gas industry manager who has the responsibility for the development of waste or potentially contaminated soil and groundwater data or must make decisions based on such data for the management or remediation of these materials. It explores the pse of common analytical chemistry instrumentation and associated techniques for identification of environmentally hazardous materials. Sufficient detail is given to familiarize the nontechnical reader with the principles behind the operation of each technique. The scope and realm of the techniques and their constituent variations are portrayed through a discussion of crucial details and, where appropriate, the depiction of real-life data. It is the author's intention to provide an easily understood handbook for gas industry management. Techniques which determine the presence, composition, and quantification of gas industry wastes are discussed. Greater focus is given to traditional techniques which have been the mainstay of modem analytical benchwork. However, with the continual advancement of instrumental principles and design, several techniques have been included which are likely to receive greater attention in fiture considerations for waste-related detection. Definitions and concepts inherent to a thorough understanding of the principles common to analytical chemistry are discussed. It is also crucial that gas industry managers understand the effects of the various actions which take place before, during, and after the actual sampling step. When a series of sample collection, storage, and transport activities occur, new or inexperienced project managers may overlook or misunderstand the importance of the sequence. Each step has an impact on the final results of the measurement process; errors in judgment or decision making can be costly. Specific techniques and methodologies for the collection, storage, and transport of environmental media samples are not described or

Soil aeration is an important factor for the biogeochemistry of soils. Generally, gas exchange between soil and atmosphere is assumed to be governed by molecular diffusion and by this way fluxes can be calculated using by Fick's Law. The soil gas diffusion coefficient DS represents the proportional factor between the gas flux and the gas concentration gradient in the soil and reflects the ability of the soil to "transport passively" gas through the soil. One common way to determine DS is taking core samples in the field and measuring DS in the lab. Unfortunately this method is destructive and laborious and it can only reflect a small fraction of the whole soil. As a consequence, uncertainty about the resulting effective diffusivity on the profile scale, i.e. the real aeration status remains. We developed a method to measure and monitor DS in situ. The set-up consists of a custom made gas sampling device, the continuous injection of an inert tracer gas and inverse gas transport modelling in the soil. The gas sampling device has seven sampling depths (from 0 to -43 cm of depth) and can be easily installed into vertical holes drilled by an auger, which allows for fast installation of the system. Helium (He) as inert tracer gas was injected continuously at the lower end of the device. The resulting steady state distribution of He was used to deduce the DS depth distribution of the soil. For Finite Element Modeling of the gas-sampling-device/soil system the program COMSOL was used. We tested our new method both in the lab and in a field study and compared the results with a reference lab method using soil cores. DS profiles obtained by our in-situ method were consistent with DS profiles determined based on soil core analyses. Soil gas profiles could be measured with a temporal resolution of 30 minutes. During the field study, there was an important rain event and we could monitor the decrease in soil gas diffusivity in the top soil due to water infiltration. The effect

Noble-gas isotopic abundances were determined in 36 recently recovered chondrites including 27 chondrites recovered in China. The comparison of the release patterns of trapped noble gases from ordinary and from carbonaceous chondrites showed that the planetary trapped noble gases in ordinary chondrites were released mainly above 1200 C, whereas more than 85 percent of noble gases trapped in carbonaceous chondrites were released at or below 1200 C, indicating that the carrier phases of the trapped noble gases in ordinary and in carbonaceous chondrites may not be the same. It is suggested that the ordinary chondrites started to retain fission Xe about 48 +/- 30 Ma earlier than Angra dos Reis. No systematic differences were observed between H, L, and LL or type 5 and 6 chondrites with respect to the time of fission Xe retention. Eight chondrites displayed neutron capture effects due to secondary cosmic-ray-produced neutrons.

The ultrafast dynamics of micro-plasmas generated by an ˜80 fs laser pulse in noble gases has been investigated using four-wave mixing (FWM). The evolution patterns of the FWM signal are indicative of the gas species and ambient conditions. The signal is observed to reach higher intensity levels faster for Xe, with progressively lower scattering intensity and longer time dynamics for the noblegas series Xe, Kr, Ar, Ne, and He. The theoretical model for interpreting this temporal dynamics is based on initial tunnel ionization followed by electron impact ionization cooling. The model reproduces well the measured degree of ionization in atmospheric-pressure laser-induced plasmas and predicts quantitatively the intensity of four-wave mixing as a function of time for the series of five noble gases. The model also predicts the dynamics as a function of pump laser intensity and gas pressure. The findings open the way for effective control of micro-plasma dynamics.

A method for conducting laser absorption measurements in high temperature process streams having high levels of particulate matter is disclosed. An impinger is positioned substantially parallel to a laser beam propagation path and at upstream position relative to the laser beam. Beam shielding pipes shield the beam from the surrounding environment. Measurement is conducted only in the gap between the two shielding pipes where the beam propagates through the process gas. The impinger facilitates reduced particle presence in the measurement beam, resulting in improved SNR (signal-to-noise) and improved sensitivity and dynamic range of the measurement.

This paper presents the work of using advanced optical measurement techniques to implement stack gas emission monitoring and process control. A system is designed to conduct online measurement of SO2/NOX and mercury emission from stacks and slipping NH3 of de-nitrification process. The system is consisted of SO2/NOX monitoring subsystem, mercury monitoring subsystem, and NH3 monitoring subsystem. The SO2/NOX monitoring subsystem is developed based on the ultraviolet differential optical absorption spectroscopy (UV-DOAS) technique. By using this technique, a linearity error less than +/-1% F.S. is achieved, and the measurement errors resulting from optical path contamination and light fluctuation are removed. Moreover, this subsystem employs in situ extraction and hot-wet line sampling technique to significantly reduce SO2 loss due to condensation and protect gas pipeline from corrosion. The mercury monitoring subsystem is used to measure the concentration of element mercury (Hg0), oxidized mercury (Hg2+), and total gaseous mercury (HgT) in the flue gas exhaust. The measurement of Hg with a low detection limit (0.1μg/m3) and a high sensitivity is realized by using cold vapor atom fluorescence spectroscopy (CVAFS) technique. This subsystem is also equipped with an inertial separation type sampling technique to prevent gas pipeline from being clogged and to reduce speciation mercury measurement error. The NH3 monitoring subsystem is developed to measure the concentration of slipping NH3 and then to help improving the efficiency of de-nitrification. The NH3 concentration as low as 0.1ppm is able to be measured by using the off-axis integrated cavity output spectroscopy (ICOS) and the tunable diode laser absorption spectroscopy (TDLAS) techniques. The problem of trace NH3 sampling loss is solved by applying heating the gas pipelines when the measurement is running.

The computer monitoring system applied in the electric and thermal power plant in Kawȩczyn is described. Requirements for a computer monitoring and control system in an industrial flue gas cleaning plant is also presented.

This paper presents research into the adaptation of monitoring techniques from maintainability and reliability (M&R) engineering for remote unattended monitoring of gas centrifuge enrichment plants (GCEPs) for international safeguards. Two categories of techniques are discussed: the sequential probability ratio test (SPRT) for diagnostic monitoring, and sequential Monte Carlo (SMC or, more commonly, particle filtering ) for prognostic monitoring. Development and testing of the application of condition-based monitoring (CBM) techniques was performed on the Oak Ridge Mock Feed and Withdrawal (F&W) facility as a proof of principle. CBM techniques have been extensively developed for M&R assessment of physical processes, such as manufacturing and power plants. These techniques are normally used to locate and diagnose the effects of mechanical degradation of equipment to aid in planning of maintenance and repair cycles. In a safeguards environment, however, the goal is not to identify mechanical deterioration, but to detect and diagnose (and potentially predict) attempts to circumvent normal, declared facility operations, such as through protracted diversion of enriched material. The CBM techniques are first explained from the traditional perspective of maintenance and reliability engineering. The adaptation of CBM techniques to inspector monitoring is then discussed, focusing on the unique challenges of decision-based effects rather than equipment degradation effects. These techniques are then applied to the Oak Ridge Mock F&W facility a water-based physical simulation of a material feed and withdrawal process used at enrichment plants that is used to develop and test online monitoring techniques for fully information-driven safeguards of GCEPs. Advantages and limitations of the CBM approach to online monitoring are discussed, as well as the potential challenges of adapting CBM concepts to safeguards applications.

Continuous emissions monitoring of gas turbine engines in pipeline service have typically been monitored using either laboratory derived instruments (CEMS), or predicted using data from low cost sensors on the engines and algorithms generated by mapping engine performance (PEMS). A new cost-effective system developed under a program sponsored by the Gas Research Institute (Chicago) combines the advantages of both systems to monitor engine emissions in gas transmission service. This hybrid system is a sensor-based analyzer that uses a sensor array, including a newly developed NO{sub x} sensor, to directly monitor NO{sub x}, CO, and O{sub 2} emissions at the stack. The gases are measured hot and wet. The new systems were installed and tested on a gas-fired Rolls Royce Spey turbine engine and on Ingersoll-Rand KVG-410 and Cooper GMVH-10 reciprocating engines in gas transmission service. These systems passed the Relative Accuracy Test (Part B) required under US EPA regulations (40 CFR 60).

Describes an interface that uses semiconductor metal oxides to detect low gas concentrations. Notes the detector has long life, high stability, good reproducibility, low cost, and is able to convert the gas concentration to an electrical signal with a simple circuit. Theory, schematic, and applications are provided. (MVL)

The ultrafast dynamics of microplasmas generated by femtosecond laser pulses in noble gases has been investigated using four-wave mixing (FWM). The time dependence of the FWM signal is observed to reach higher intensity levels faster for Xe, with progressively lower scattering intensity and longer time dynamics for the noblegas series Xe, Kr, Ar, Ne, and He. The temporal dynamics is interpreted in terms of a tunnel ionization and impact cooling mechanism. A formalism to interpret the observed phenomena is presented here with comparison to the measured laser intensity and gas pressure trends.

Theoretical considerations and experimental results regarding a unique class of vapor sensors are presented, and the sensors are compared to semiconductor-based sensors. The electrochemical sensors are based on nonaquaeous electrolytes, and gas-detection selectivity achieved by applying a known potential to the sensing electrode using a reference electrode and a counter electrode. Results are given regarding the detection of oxygen and carbon dioxide using one cell, the detection of 3-percent carbon dioxide in nitrogen, and the detection of carbon dioxide in air at percentages ranging from 3 to 6. The sensors are found to be effective in the detection of toxic chemical species including CO, NO2, and formaldehyde; the sensors are further found to require minimal power, operate over long periods of time, and function over a wide temperature range.

The Defense Waste Processing Facility, DWPF, has requested that the Savannah River National Laboratory, SRNL, investigate the factors that contribute to hydrogen generation to determine if current conservatism in setting the DWPF processing window can be reduced. A phased program has been undertaken to increase understanding of the factors that influence hydrogen generation in the DWPF Chemical Process Cell, CPC. The hydrogen generation in the CPC is primarily due to noble metal catalyzed decomposition of formic acid with a minor contribution from radiolytic processes. Noble metals have historically been added as trim chemicals to process simulations. The present study investigated the potential conservatism that might be present from adding the catalytic species as trim chemicals to the final sludge simulant versus co-precipitating the noble metals into the insoluble sludge solids matrix. Two sludge simulants were obtained, one with co-precipitated noble metals and one without noble metals. Co-precipitated noble metals were expected to better match real waste behavior than using trimmed noble metals during CPC simulations. Portions of both sludge simulants were held at 97 C for about eight hours to qualitatively simulate the effects of long term storage on particle morphology and speciation. The two original and two heat-treated sludge simulants were then used as feeds to Sludge Receipt and Adjustment Tank, SRAT, process simulations. Testing was done at relatively high acid stoichiometries, {approx}175%, and without mercury in order to ensure significant hydrogen generation. Hydrogen generation rates were monitored during processing to assess the impact of the form of noble metals. The following observations were made on the data: (1) Co-precipitated noble metal simulant processed similarly to trimmed noble metal simulant in most respects, such as nitrite to nitrate conversion, formate destruction, and pH, but differently with respect to hydrogen generation: (A

Core-shell particles encapsulated by a thin film of a catalytically active metal are described. The particles are preferably nanoparticles comprising a non-noble core with a noble metal shell which preferably do not include Pt. The non-noble metal-noble metal core-shell nanoparticles are encapsulated by a catalytically active metal which is preferably Pt. The core-shell nanoparticles are preferably formed by prolonged elevated-temperature annealing of nanoparticle alloys in an inert environment. This causes the noble metal component to surface segregate and form an atomically thin shell. The Pt overlayer is formed by a process involving the underpotential deposition of a monolayer of a non-noble metal followed by immersion in a solution comprising a Pt salt. A thin Pt layer forms via the galvanic displacement of non-noble surface atoms by more noble Pt atoms in the salt. The overall process is a robust and cost-efficient method for forming Pt-coated non-noble metal-noble metal core-shell nanoparticles.

Temperature distribution is a critical indicator of the health condition for Liquefied Petroleum Gas (LPG) storage tanks. In this paper, we present a large-scale wireless temperature monitoring system to evaluate the safety of LPG storage tanks. The system includes wireless sensors networks, high temperature fiber-optic sensors, and monitoring software. Finally, a case study on real-world LPG storage tanks proves the feasibility of the system. The unique features of wireless transmission, automatic data acquisition and management, local and remote access make the developed system a good alternative for temperature monitoring of LPG storage tanks in practical applications. PMID:26393596

Temperature distribution is a critical indicator of the health condition for Liquefied Petroleum Gas (LPG) storage tanks. In this paper, we present a large-scale wireless temperature monitoring system to evaluate the safety of LPG storage tanks. The system includes wireless sensors networks, high temperature fiber-optic sensors, and monitoring software. Finally, a case study on real-world LPG storage tanks proves the feasibility of the system. The unique features of wireless transmission, automatic data acquisition and management, local and remote access make the developed system a good alternative for temperature monitoring of LPG storage tanks in practical applications. PMID:26393596

A comparison of two methods of gas chromatography mass spectrometry (GCMS) and a nondispersive infrared technique, photoacoustic radiometry (PAR), is presented in the context of field monitoring a disposal site. First is presented an historical account describing the site and early monitoring to provide an overview. The intent and nature of the monitoring program changed when it was proposed to expand the Radiological Waste Site close to the Hazardous Waste Site. Both the sampling methods and analysis techniques were refined in the course of this exercise.

This thesis deals with design and implementation of a high-resolution metering system for residential natural gas meters. Detailed experimental measurements are performed on the meter to characterize and understand its measurement properties. Results from these experiments are used to develop a simple, fast and accurate technique to non-intrusively monitor the gas consumption of individual appliances in homes by resolving small amounts of gas usage. The technique is applied on an existing meter retrofitted with a module that includes a high-resolution encoder to collect gas flow data and a microprocessor to analyze and identify appliance load profiles. This approach provides a number of appealing features including low cost, easy installation and integration with automated meter reading (AMR) systems. The application of this method to residential gas meters currently deployed is also given. This is done by performing a load simulation on realistic gas loads with the aim of identifying the necessary parameters that minimize the cost and complexity of the mechanical encoder module. The primary benefits of the system are efficiency analysis, appliance health monitoring and real-time customer feedback of gas usage. Additional benefits of include the ability to detect very small leaks and theft. This system has the potential for wide scale market adoption.

Nitrous oxide emissions from wastewater treatment plants are currently measured by online gas phase analysis or grab sampling from the liquid phase. In this study, a novel method is presented to monitor the liquid phase N2O concentration for aerated as well as non-aerated conditions/reactors, following variations both in time and in space. The monitoring method consists of a gas stripping device, of which the measurement principle is based on a continuous flow of reactor liquid through a stripping flask and subsequent analysis of the N2O concentration in the stripped gas phase. The method was theoretically and experimentally evaluated for its fit for use in the wastewater treatment context. Besides, the influence of design and operating variables on the performance of the gas stripping device was addressed. This method can easily be integrated with online off-gas measurements and allows to better investigate the origin of the gas emissions from the treatment plant. Liquid phase measurements of N2O are of use in mitigation of these emissions. The method can also be applied to measure other dissolved gasses, such as methane, being another important greenhouse gas. PMID:25573615

Noble-gas hydrides HNgY are frequently described as a single ionic form (H-Ng)(+)Y(-). We apply natural bond orbital (NBO) and natural resonance theory (NRT) analyses to a series of noble-gas hydrides HNgY (Ng = He, Ne, Ar, Kr, Xe, Rn; Y = F, Cl, Br, I) to gain quantitative insight into the resonance bonding of these hypervalent molecules. We find that each of the studied species should be better represented as a resonance hybrid of three leading resonance structures, namely, H-Ng(+ -):Y (I), H:(- +)Ng-Y (II), and H^Y (III), in which the "ω-bonded" structures I and II arise from the complementary donor-acceptor interactions nY → σ*HNg and nH → σ*NgY, while the "long-bond" ([small sigma, Greek, circumflex]-type) structure III arises from the nNg → [small sigma, Greek, circumflex]*HY/[small sigma, Greek, circumflex]HY interaction. The bonding for all of the studied molecules can be well described in terms of the continuously variable resonance weightings of 3c/4e ω-bonding and [small sigma, Greek, circumflex]-type long-bonding motifs. Furthermore, we find that the calculated bond orders satisfy a generalized form of "conservation of bond order" that incorporates both ω-bonding and long-bonding contributions [viz., (bHNg + bNgY) + bHY = bω-bonding + blong-bonding = 1]. Such "conservation" throughout the title series implies a competitive relationship between ω-bonding and [small sigma, Greek, circumflex]-type long-bonding, whose variations are found to depend in a chemically reasonable manner on the electronegativity of Y and the outer valence-shell character of the central Ng atom. The calculated bond orders are also found to exhibit chemically reasonable correlations with bond lengths, vibrational frequencies, and bond dissociation energies, in accord with Badger's rule and related empirical relationships. Overall, the results provide electronic principles and chemical insight that may prove useful in the rational design of noble-gas hydrides of

In the mine pit using the "U" ventilation systems, there is serious gas accumulating phenomenon nearby upper corner. If not effectively in time, the serious coal mine security accident will exist because of the gas ultra to limit. Through analysis to the gas accumulation reason and the distribution rule nearby upper corner, the situation is understood that the wind speed is extremely low near upper corner region and some parts is at eddy flow status; Using the practical and economical real-time monitoring system, accumulative gas can be scattered through the air flow perturbation of hydraulic blower. This method could reduce partial gas concentration of upper corner in order to meet the coal mine security production requirements

In this report we discuss the performance in real condition of an optical based real-time NO2 gasmonitoring system. For detecting the gas concentration in the ambient air we have developed an optical sensor based on one-dimensional photonic crystal with two defects that allows the existence of photonic pass band inside the associated photonic band gap. To measure the gas concentration, we dissolve the corresponding NO2 gas into a specific Griess Saltzman reagent solution. The change of gas concentration in the related dissolved-solution can be inspected by the photonic pass band peak variation. It is observed that the wavelength of the photonic pass band peak of the fabricated photonic crystal is nearly coincide with the wavelength of the associated solution highest absorbance. The laboratory test shows that the device works properly, whereas the field measurement test demonstrates accurate results with validation error of 1.56%.

On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

The paper discusses greenhouse gas (GHG) mitigation and monitoring technology performance activities of the GHG Technology Verification Center. The Center is a public/private partnership between Southern Research Institute and the U.S. EPA's Office of Research and Development. It...

This document provides a general overview of the computer systems software that perform the data acquisition and control for the 241-SY-101 GasMonitoring System II (GMS-2). It outlines the system layout, and contains descriptions of components and the functions they perform. The GMS-2 system was designed and implemented by Los Alamos National Laboratory and supplied to Westinghouse Hanford Company

In this work we begin to examine the feasibility of using time-lapse seismic methods-specifically the vertical seismic profiling (VSP) method-for monitoring changes in hydrate accumulations that are predicted to occur during production of natural gas.

Despite their great importance in low-temperaturegeochemistry, self-diffusion coefficients of noblegas isotopes in liquidwater (D) have been measured only for the major isotopes of helium, neon,krypton and xenon. Data on the self-diffusion coefficients of minor noblegas isotopes are essentially non-existent and so typically are estimatedby a kinetic theory model in which D varies as the inverse square root ofthe isotopic mass (m): D proportional to m-0.5. To examine the validityof the kinetic theory model, we performed molecular dynamics (MD)simulations of the diffusion of noble gases in ambient liquid water withan accurate set of noblegas-water interaction potentials. Our simulationresults agree with available experimental data on the solvation structureand self-diffusion coefficients of the major noblegas isotopes in liquidwater and reveal for the first time that the isotopic mass-dependence ofall noblegas self-diffusion coefficients has the power-law form Dproportional to m-beta with 0noble gasisotopes caused by diffusion in ambient liquid water.

Seafloor observatories have been installed at the Cascadia margin with a long-term (>20 year) lifespan. These observatories consist of a variety of node locations cabled back to shore for continuous power and communication to instruments via high bandwidth internet access. Ocean Networks Canada (ONC) maintains two hydrate sites at Barkley Canyon and Clayoquot Slope off Vancouver Island, and the Ocean Observatories Initiative (OOI) Cabled Array connects to Hydrate Ridge off the Oregon coast. Together, these installations comprise a diverse suite of different experiments. For example, a seafloor crawler, operated by Jacobs University in Bremen, travels around the Barkley hydrate mounds on a daily basis and carries out a suite of measurements such as determining the rate of change of the benthic community composition. Another example is from several years of hourly sonar data showing gas bubbles rising from the seafloor near the Bullseye Vent with varying intensities, allowing statistically sound correlations with other seafloor parameters such as ground shaking, temperature and pressure variations and currents, where tidal pressure appearing as the main driver. The Southern Hydrate Ridge is now equipped with the world's first long-term seafloor mass spectrometer, co-located with a camera and lights, hydrophone, current meters, pressure sensor, autonomous dissolved oxygen and fluid samplers, and is surrounded by a seismometer array for local seismicity. In the future, long-term data will be continuously captured and made available throughout the year covering the full range of variations of the dynamic hydrate system, and expect additional experiments to be connected to the observatories from the broader research community.

Atmospheric transport inversion is commonly used to infer greenhouse gas (GHG) flux estimates from concentration measurements. The optimal location of ground-based observing stations that supply these measurements can be determined by network design. Here, we use a Lagrangian particle dispersion model (LPDM) in reverse mode together with a Bayesian inverse modelling framework to derive optimal GHG observing networks for Australia. This extends the network design for carbon dioxide (CO2) performed by Ziehn et al. (2014) to also minimise the uncertainty on the flux estimates for methane (CH4) and nitrous oxide (N2O), both individually and in a combined network using multiple objectives. Optimal networks are generated by adding up to five new stations to the base network, which is defined as two existing stations, Cape Grim and Gunn Point, in southern and northern Australia respectively. The individual networks for CO2, CH4 and N2O and the combined observing network show large similarities because the flux uncertainties for each GHG are dominated by regions of biologically productive land. There is little penalty, in terms of flux uncertainty reduction, for the combined network compared to individually designed networks. The location of the stations in the combined network is sensitive to variations in the assumed data uncertainty across locations. A simple assessment of economic costs has been included in our network design approach, considering both establishment and maintenance costs. Our results suggest that, while site logistics change the optimal network, there is only a small impact on the flux uncertainty reductions achieved with increasing network size.

We report noblegas data of helium (He), neon (Ne), argon (Ar), krypton (Kr) and xenon (Xe), cosmic ray exposure (CRE) ages and nominal gas retention (K-Ar, U-Th-He) ages for seven howardites (CRE 01400, EET 87513, EET 87518, EET 99400, GRO 95535, GRO 95602, SAN 03472), in continuing research to identify regolithic samples, and better understand the vestan regolith. In our previous work, we found little correlation between suggested regolith parameters of Ni > 300 μg/g, Al2O3 8-9 wt% and eucrite/diogenite (E:D) ratio of 2:1 (Warren et al., 2009), and trapped solar wind (SW), fractionated solar wind (FSW) or planetary noblegas components (from impacted material) - noblegas indicators of a regolithic origin. Here, we have expanded our data set to include samples outside of these parameters to further explore composition, and the differences in Ni content as indicators for the presence of non-Vesta material. In addition, our sample set includes two potentially paired meteorites from the GRO suite. Finally, in our petrographic studies, the samples selected showed no evidence for carbonaceous chondrite fragments, which should reduce the effect of “contamination” by planetary noblegas components, and will allow us to better identify SW/FSW components, where present. Of the samples studied here, three howardites GRO 95535, GRO 95602 and EET 87513 show evidence for a regolithic origin, with both isotopic and element noblegas ratios clearly pointing to the presence of trapped components similar to SW/FSW or planetary. The two GRO howardites, GRO 95535 and GRO 95602, show similar noblegas ratios to our previously defined SW/FSW dominated regolithic group (LEW 85313 and MET 00423), suggesting a surface origin for these samples. However, interestingly, the GRO samples show vastly different cosmogenic noblegas abundances, and thus different CRE ages, which suggests that they are not paired. For howardite EET 87513, the data hint to the presence of CM-material, with a

Among the lunar soil constituents, monomineralic grains deserve special attention. Noble gases of carefully prepared mineral separates from lunar bulk soils were studied. The major results and conclusions of these investigations are summarized, in the context of both the regolith evolution and the history of the solar corpuscular radiation. With regard to the most abundant noblegas component in the regolith samples (the solar gases) the mineral grains have mainly two properties giving these particles among all soil constituents the best characteristics as sensors for solar gases, despite the fact, that the noblegas concentrations in a mineral separate are 10 to 60 times lower that those in a bulk sample of the same grain size. The first of these properties is the mineral dependent retentivity of the light gases He and Ne, the second property concerns the relatively short time during which a mineral grain acquires it solar gases. These two points are briefly discussed.

Hydrothermal vent fluids collected with the DSRV Alvin from the southern limb of the Juan de Fuca Ridge are chemically unique, having chloride concentrations {approximately}2 times ambient seawater. The same fluids contain noble gases in relative abundances like 2{degree}C air-saturated seawater, the expected recharge composition. However, the absolute noblegas abundances are depleted by {approximately}30% relative to seawater. The combination of very high chloride and moderately depleted noble gases appears to require formation of a Cl-rich, gas-free brine by phase separation. This brine is mixed with recharge seawater at temperatures in excess of {approximately}340{degree}C and, therefore, deep in the hydrothermal system.

It is trend to build an intense neutrino beam facility for the fundamental physics research, e.g. LBNF at Fermilab, T2K at KEK, and CNGS at CERN. They have investigated a hadron monitor to diagnose the primary/secondary beam quality. The existing hadron monitor based on an ionization chamber is not robust in the high-radiation environment vicinity of MW-class secondary particle production targets. We propose a gas-filled RF resonator to use as the hadron monitor since it is simple and hence radiation robust in this environment. When charged particles pass through the resonator they produce ionized plasma via the Coulomb interaction with the inert gas. The beam-induced plasma changes the permittivity of inert gas. As a result, a resonant frequency in the resonator shifts with the amount of ionized electrons. The radiation sensitivity is adjustable by the inert gas pressure and the RF amplitude. The hadron profile will be reconstructed with a tomography technique in the hodoscope which consists of X, Y, and theta layers by using a strip-shaped gas resonator. The sensitivity and possible system design will be shown in this presentation.

Aerogels or xerogels containing atomically dispersed noble metals for applications such as environmental remediation are disclosed. New noble metal precursors, such as Pt--Si or Pd(Si--P){sub 2}, have been created to bridge the incompatibility between noble metals and oxygen, followed by their incorporation into the aerogel or xerogel through sol-gel chemistry and processing. Applications include oxidation of hydrocarbons and reduction of nitrogen oxide species, complete oxidation of volatile organic carbon species, oxidative membranes for photocatalysis and partial oxidation for synthetic applications.

Aerogels or xerogels containing atomically dispersed noble metals for applications such environmental remediation. New noble metal precursors, such as Pt--Si or Pd(Si--P).sub.2, have been created to bridge the incompatibility between noble metals and oxygen, followed by their incorporation into the aerogel or xerogel through sol-gel chemistry and processing. Applications include oxidation of hydrocarbons and reduction of nitrogen oxide species, complete oxidation of volatile organic carbon species, oxidative membranes for photocatalysis and partial oxidation for synthetic applications.

Liquid noble gases are increasingly used as active detector materials in particle and nuclear physics. Applications include calorimeters and neutrino oscillation experiments as well as searches for neutrinoless double beta decay, direct dark matter, muon electron conversion, and the neutron electric dipole moment. One of the great advantages of liquid noble gases is their copious production of ultraviolet scintillation light, which contains information about event energy and particle type. I will review the scintillation properties of the various liquid noble gases and the means used to collect their scintillation light, including recent advances in photomultiplier technology and wavelength shifters.

Noble metals in fission products are of strategic value. Market prices for noble metals are rising more rapidly than recovery costs. A promising concept has been developed for recovery of noble metals from fission product waste. Although the assessment was made only for the three noble metal fission products (Rh, Pd, Ru), there are other fission products and actinides which have potential value. (DLC)

As part of Ocean Drilling Program Leg 204 at southern Hydrate Ridge off Oregon we have monitored changes in sediment electrical resistivity during controlled gas hydrate dissociation experiments. Two cores were used, each filled with gas hydrate bearing sediments (predominantly mud/silty mud). One core was from Site 1249 (1249F-9H3), 42.1 m below seafloor (mbsf) and the other from Site 1248 (1248C-4X1), 28.8 mbsf. At Site 1247, a third experiment was conducted on a core without gas hydrate (1247B-2H1, 3.6 mbsf). First, the cores were imaged using an infra-red (IR) camera upon recovery to map the gas hydrate occurrence through dissociation cooling. Over a period of several hours, successive runs on the multi-sensor track (includes sensors for P-wave velocity, resistivity, magnetic susceptibility and gamma-ray density) were carried out complemented by X-ray imaging on core 1249F-9H3. After complete equilibration to room temperature (17-18??C) and complete gas hydrate dissociation, the final measurement of electrical resistivity was used to calculate pore-water resistivity and salinities. The calculated pore-water freshening after dissociation is equivalent to a gas hydrate concentration in situ of 35-70% along core 1249F-9H3 and 20-35% for core 1248C-4X1 assuming seawater salinity of in situ pore fluid. Detailed analysis of the IR scan, X-ray images and split-core photographs showed the hydrate mainly occurred disseminated throughout the core. Additionally, in core 1249F-9H3, a single hydrate filled ve